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

Table 1 shows a summary of the commercial technologies used


1.1. Heavy oil resources for heavy oil and residue upgrading and their processing capacity.
Carbon rejection processes represent 56.6% of the total worldwide
There are very large heavy oil, extra-heavy oil, and bitumen re- processing capacity mainly due to its relative low investment. In
sources whose extent and locations are well known. The Interna- contrast to other countries, Japan refineries prefer the use of
tional Energy Agency (IEA) estimates that there are 6 trillion fixed-bed hydrotreating technologies.
(6  1012) barrels in place worldwide; with 2.5  1012 bbl in Wes- The increasing trend of crude prices leads the hydrogen addi-
tern Canada, 1.5  1012 bbl in Venezuela, 1  1012 bbl in Russia, tion processes to be more attractive in terms of profitability acquir-
and 100–180  109 bbl in the United States. Most of these re- ing higher yields and quality. This tendency will probably increase
sources are currently untapped [2]. the capacity of those processes in the world.
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 2. Technologies for upgrading of heavy oils
and to the refineries, and consequently low processing capacity
in the refineries. Heavy oils have relatively low economic values and are more
For these reasons, it is mandatory to upgrade the heavy crude difficult to process than conventional crudes, i.e. light crude oils.
oil, if either upstream or downstream sectors are looking for bigger Heavy oils, however, can be upgraded with available refining tech-
benefits during the heavy petroleum production and refining. For nologies to improve transportability and increase their value. The
high resid content of heavy oils makes them candidates for upgrad-
⇑ Corresponding author. Tel./fax: +52 55 9175 8429. ing processes that increase the hydrogen-to-carbon ratio [5].
E-mail addresses: lcastane@imp.mx (L.C. Castañeda), jancheyt@imp.mx A number of technologies has been developed over the years for
(J. Ancheyta). 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 of 375000 bbl/d and one more under construction with vacuum
routes [6,7]. residue capacity of 95000 bbl/d in Alberta, Canada. In fluid-coking
Carbon rejection is one of the first type of conversion processes about 6% of coke, basis feed, is burned to supply heat for the pro-
applied to the oil industry, and has been used since 1913, when dif- cess while the net coke yield is 70–75% of that from delayed
ferent fuels and heavy hydrocarbons were heated under pressure coking.
in large drums until reaching their thermal fracture into lower Flexicoking was commercialized to gasify the coke with steam
molecular size products with a lower boiling point; at the same and air in a separate gasifier vessel to produce a low-Btu fuel gas
time, some of those molecules reacted among themselves to form with a heating value of 125–130 Btu/scf. Five units with a total
others even larger than the original ones, giving origin to the coke. capacity of 179000 bbl/d were constructed from 1976 to 1986.
In general, thermal cracking of residue is carried out at rela- Gas and liquid yields are the same as for fluid-coking but up to
tively moderate pressures and it is often called coking process. 97% of the coke can be gasified.
Coking process transfers hydrogen from the heavy molecules to The technology for residue gasification to produce synthesis gas
the lighter molecules, resulting in the production of coke or carbon. for hydrogen or chemicals, or for combined cycle power generation
Visbreaking is a widely-known carbon rejection technology that is being applied mainly in Europe where coking of residues is not
consists of a thermal cracking process to produce naphtha and extensive.
other distillates, with a residue product that is visco-reduced (less Hydrogen addition technologies produce high yield of products
viscous than the initial feed). Visbreaking, thermal cracking, and and upgraded crude oil with a commercial value higher than that
coking technologies can be generally applied to all residues, be- of the carbon rejection technologies, but require larger investment
cause they are not limited to constraints such as metal content and more natural gas availability to produce the required amount
and coke forming tendencies as in the case of catalytic processes of hydrogen, particularly those working at high reaction severity
for upgrading. conditions, e.g. H-Oil and LC-Fining processes. This family of pro-
Fluid-coking and flexicoking are developments of Exxon Mobil cesses upgrades heavy oils by adding hydrogen, thus increasing
Research & Engineering. Fluid-coking that was commercialized in the hydrogen-to-carbon ratio of the products (reducing their den-
the early 1950s, has eight built units with a combined capacity 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, preparation of finished lubricants, as well as feed of catalytic crack-
e.g. fixed-bed, moving-bed, ebullated-bed and slurry-bed ing or hydrocracking plants, whereas the residue is used to prepare
processes. asphalts and also as feed for thermal cracking processes. SDA pro-
More recently a moderate reaction severity process has been cess offers the additional option of producing a low cost feed for
proposed for upgrading of heavy oils and residue, which has as the gasification process. SDA is an advantageous process because
main advantage low investment and operating costs while produc- of its relatively low costs and the implicit possibility of obtaining
ing high API gravity, low impurity content upgraded oil without a wide variety of deasphalted oils. It also offers a high selectivity
excessive sediments formation problems [8]. for asphaltenes, a considerable metal rejection, a certain selectivity
Fig. 2 shows a general comparison of various upgrading tech- to reject carbon and minor selectivity for sulfur and nitrogen. Its
nologies taking into account operating temperature and pressure. disadvantages are the lack of residue conversion and the high vis-
The asphaltenes and metals in the feedstock of these technologies cosity of the asphalt produced. There are currently more than 50
have an important role towards the selection of the type of reactor commercial units, based on the FW–UOP technology. The solvent
[9]. extraction processes are classified into two groups, the conven-
tional ones and those operating at super-critical conditions. The
2.1. Solvent deasphalting (SDA) operational philosophy in both cases is the same, and the only dif-
ference is the process conditions, which are set to optimize the sol-
This is a physical separation process where the vacuum residue vent handling and the operation efficiency, such as the Demex
is divided into its components by means of a solvent used as conventional and Rose supercritical processes.
absorption medium [10–13]. It is a process based on specific grav-
ity as opposed to the boiling point distillation. Its products are 2.2. Visbreaking (VB)
deasphalted oil (DAO), and a residue (pitch) rich in aromatics with
high concentration of impurities such as metals, sulfur, asphalt- Visbreaking is one of the lowest cost conversion process
enes and Conradson carbon. DAO can be used as a base for the 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) 110–127 113

resid to reduce its viscosity and produce some distillates. With vac- 2.5. Flexi-coking (FXC)
uum resid feed, typically about 20% is converted into distillate and
lighter products [14,15]. This is a process developed also by Exxon Mobil as a modifica-
In 1993, Foster Wheeler and Universal Oil Products made an tion to FCK, adding a step for coke gasifying to produce flexi-gas, a
agreement to combine their technical experiences, knowledge coke gas with a low heating power (80–100 BTU/cf), reducing con-
and resources in the visco-reduction area. In total, these companies siderably the coke production. It provides higher flexibility yield-
have developed over 50 visco-reduction plants, 20 after the agree- ing two clean products: liquids and flexi-gas. Product yield is
ment. The key parameter of VB process is product viscosity. Fol- similar to that of FCK, but coke production is reduced from 24%
lowing a preheating step, the feed is sent to an oven where the to 4%, converting it into flexi-gas. Essentially petroleum coke is
cracking temperature is reached. Although the cracking process eliminated and an economical fuel gas is available for consuming
starts in the oven, the major part of it takes place within a reaction in refinery. Due to the high initial investment, and mechanical cost,
chamber located immediately after the oven. The cracked material only five units have been built around the world [25,26].
is cooled down to avoid excessive formation of coke, and then is The first FXC unit was put in service in Japan in 1976 further ex-
sent to a fractionation unit for product separation. Similarly to panded in 2002. Currently, Hellenic Petroleum is constructing a
FW and UOP, Shell and ABB-Lummus have been dedicated to the 21 MBD unit in Elefsis, Greece with an investment higher than
development and commercialization of a drum type application 1000 MM Euros, while another unit of 22 MBD is licensed for Petro
namely Reaction Chamber (Soaker), with over 80 projects based Peru [26,27].
on this process, many of them already in service [16,17].
2.6. Gasification (GF)
2.3. Delayed Coking (DC)
The Texaco Gasification Process (TGP) developed in the late
Delayed coking uses thermal cracking to convert petroleum res- 1940s, was projected to produce hydrogen and carbon monoxide
idue into higher value distillate products and coke without the pro- – syngas – for chemical plant and refinery applications. It was de-
duction of fuel oil. The general goal of such a technology is to signed to process natural gas. In the 1950s, it was modified for hea-
maximize distillate yield while minimizing coke production. De- vy oil feeds, in the 1970s for solid feeds like coal, and in the 1980s
layed coking technology is one of the most cost-effective routes for petroleum coke. Nearly from its origin, the process has been an
for converting/upgrading heavy residua. The process can handle a attractive means for hydrogen production [28,29].
variety of feedstocks, such as petroleum-derived resids, cracked Among commercially proven technologies, TGP based plants re-
materials (pyrolysis tar and cycle oils), and liquid feedstocks de- main the most environmentally benign means of generating valu-
rived from coal [18–20]. able products from sulfur-containing feedstocks. Power plants
DC is a mature commercially proven technology which operates with TGP technology emit a fraction of the NOx and SOx pollutants
at low pressure without catalyst and no hydrogen is consumed. It that are produced from conventional or fluidized bed boiler instal-
is insensitive to contaminants producing low refinery emissions lations. Even advanced boiler systems produce solid wastes in
(SO2). Disadvantages of this technology can be the abundant pro- quantities far in excess of those produced in TGP plants. Texaco
duction of coke, low yield of upgraded oil, and highly aromatic gasification converts heavy oils such as vacuum residue and
products which require post-treatment [21,22]. Foster Wheeler of- asphaltenes into synthesis gas (syngas) which is primarily hydro-
fers SYDEC (Selective Yield Delayed Coking) under license with gen and carbon monoxide. The use of gasification can help refiners
over 25 revamps designed in the last 10 years, over 20 new units produce hydrogen, enhance the yield of high-value products, elim-
designed in the last 5 years, and over 2.5 million BPSD have been inate the production of high-sulfur fuel oil, minimize the refinery’s
installed using such a technology [23]. environmental footprint, and process a wider range of crude oils,
especially those with higher sulfur content [30–32].
2.4. Fluid-coking (FCK)
2.7. Resid Fluid Catalytic Cracking (RFCC)
This is a continuous coking process developed by ExxonMobil,
which converts heavy streams, such as residua from atmospheric RFCC is a refining process to convert residua feedstocks
or vacuum distillation, bottoms of SDA and catalytic cracking units, (CCR > 4 wt.%) with low metal content into lighter, higher value
and bitumens of oil sands, into light products. Distillation residue products. The product includes light olefins such as propylene
with an initial boiling point of 1050 °F goes into the scrubbing sec- and butylenes, gasoline, and distillates, whereas coke is deposited
tion, where it exchanges heat with the vapors coming out from the on the catalyst. RFCC is a commercially proven catalytic cracking
reaction step. The condensing fraction is recycled and blended with process that can convert a wide range of virgin and pre-processed
new feed, whereas the vapors are sent to the fractionation tower. residue feedstocks [33,34]. Stone & Webster (S&W), in association
At the reaction section, the feed is thermally cracked into light with Institut Français du Petrole (IFP), is the licenser of the S&W–
products and coke; this is sent to the burner, where air and heat IFP residual fluid catalytic cracking (R2R) process. The original
are provided to burn between 15% and 25% of the total; the balance S&W–IFP R2R (reactor 2 regenerators) process was developed dur-
is sent back to the reactor to maintain the reaction temperature ing the early 1980s by Total Petroleum Inc. Today 26 IFP RFCC units
[24–26]. either revamp or grassroots have been licensed worldwide [33].
Similarly to FCC process, fluids solids are in a continuous circu- The RFCC process also works well in combination with other heavy
lation. Fluid coke circulates between burner and reactor. The coke oil conversion processes such as delayed coking and visbreaking.
combustion provides heat to the process (around 20% of produced
coke). Fluid coking yields lower coke production and easier han- 2.8. Fixed-bed hydroprocessing/hydrocracking (FBR)
dling compared with delayed coking.
The product yield of the process is in the range of 70–75% per In fixed-bed residue hydroprocessing/hydrocracking, Axens
load weight, whereas the balance is coke. Since 1954, seven units technology utilizing its Hyvahl process (using the Permutable
have been put in service worldwide, with an accumulated capacity Reactor System), has reached an important commercialization le-
of 350,000 BPD. At the beginning it was stated that FCK would re- vel. The first Hyvahl unit was put on stream in 1995 using Arabian
place DC in the market, but it has not taken place so far. 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 ditional technology are the integration of IS2 (inter-stage
50,000 bbl/d unit at the S-Oil Osan refinery in South Korea separator) between reactors in series and the application of
[35,36]. In another fixed-bed hydroprocessing commercial C2U (cascade catalyst utilization).
development, Chevron Lummus Global (CLG) licenses a family of
residuum conversion technologies such as On-stream Catalyst Totalizing H-Oil/HCC and H-Oil/RC references, there are cur-
Replacement technology (OCR) for processing high-metal feeds rently seven H-Oil units running around the world with a com-
and the effective revamp alternative, the installation of an Upflow bined capacity of about 260,000 bbl/d and 5 LC-Fining units with
Reactor (UFR). It is similar in operation to the OCR unit but without a capacity of 245,000 bbl/d. Axens also offers the T-Star process,
the on-stream catalyst replacement transfer system, which can be developed by Texaco for gas oil hydroprocessing, which is a simpli-
added at a later date. The upflow reactor has now been operated in fied version of the H-Oil process [45].
vacuum residue desulfurization service at Sinopećs Qilu Shengli The H-Oil unit located at Tula refinery, Mexico was revamped
refinery and Kuwait National Petroleum Corporation Selected from residue hydrocracker to FCC feed pretreater since 2009 [46].
CLG for Resid Upgrading Technology for Clean Fuels Project 2020
where the RDS units will utilize CLG’s UFR reactor technology 2.10. Slurry-Phase Reactor technology (SPR)
[37,38].
The third relevant fixed-bed technology (Bunker Reactor Sys- The Slurry Phase Reactor processes employ disposable catalysts
tem) was developed by Shell as HYCON Process [39]. This process whose development aimed at decreasing the cost of the catalyst
uses conventional fixed-bed reactors for hydroprocessing of low inventory, i.e. cost of the fresh hydroprocessing catalysts and that
metals content feeds. As the metals content of the feed increases, of the spent catalysts. A number of processes employing a dispos-
one or more moving bed ‘‘bunker’’ reactors are added as the lead- able catalyst are in a developmental stage and others are in a near
ing reactors for hydrodemetallization. The ‘‘bunker’’ reactors and a commercial stage [47,48].
catalyst system are designed for continuous catalyst replacement. The HDH Plus process is a technology developed in the 80s at
Catalyst is replaced at a rate to insure a total plant run time of at PDVSA-Intevep for the treatment, conversion and valorization of
least a year, typically at a rate of 0.5–2% of catalyst inventory per the Orinoco Belt heavy crudes. It took more than 20 years of re-
day depending on feed metals [40]. search and development, including scaling tests and evaluation
Shell started up a HYCON unit with ‘‘bunker’’ reactors at its of different crudes, and consists of a high conversion process of
Pernis, Netherlands refinery in 1989. After some important modifi- heavy crudes and refinery residua via hydro-conversion, from
cations, the plant has been operating since 1998 at a feed rate of 90% to 95%, versus the 70% level of the DC case [49,50]. There are
about 27,000 bbl/d of vacuum residue from Arabian and Iranian two semi commercial-scale plants under construction at the refin-
crudes. Conversion to distillates is typically 65–70%. The uncon- eries of El Palito and Puerto La Cruz in Venezuela, projected with a
verted residue is blended into a 1–2 wt.% sulfur fuel oil. capacity to convert 25,000 daily barrels of vacuum residua each,
and it has been frequently mentioned by PDVSA authorities that
2.9. Ebullated-bed hydrocracking (EBR) this technology will be used in the future upgrading complexes
of the Orinoco Belt new projects. This technology generates a con-
Ebullated-bed hydrocracking process has been used for desul- siderable yield in liquids (115 vol.%), renders high quality products
furization, demetallization, Conradson carbon reduction, and and is flexible to process different feeds with high sulfur and metal
hydroprocessing of atmospheric and vacuum residua. Feedstocks contents [51].
processed include vacuum residue comprising high sulfur and The VEBA Combi cracking process (VCC) which derived from the
heaviest high metals. Commercial designs range from desulfuriza- coal liquefaction experience in Germany is perhaps the best known
tion at minimum conversion for production of high quality fuel slurry phase process [46,52]. The plant was able to achieve 90–94%
oils, to nearly complete conversion of residue into low sulfur distil- conversion of a residue, at about 4000 b/d throughput [53]. Iron
late products. Residua product can be used as fuel oil, blended into oxide and/or partially gasified lignite char were found to be effec-
synthetic crude, or as feedstock to a coker, visbreaker, gasifier, or a tive additives. VEBA operates its unit at Bottrop, Germany for the
solvent deasphalter [41,42]. conversion of plastic disposals to light fuels.
In the ebullating bed processes, hydrocarbon feed and H2 are The CANMET Hydrocracking Process is a high conversion, high
fed upflow through a catalyst bed, expanding and backmixing the demetallizatlon, residuum hydrocracking process which, using an
bed, and minimizing bed plugging. Fresh catalyst is added to the additive to inhibit coke formation, achieves conversion of high
top of the reactor and spent catalyst is withdrawn from the bottom boiling point hydrocarbons into lighter products. It was initially
of the reactor. There are two ebullating bed processes: the H-Oil developed to upgrade tar sands bitumen and heavy oils of Cana-
process of Axens/IFP and the LC-Fining process of Chevron Lummus dian origin [54,55].
Global. The two processes are similar in concept but differ in some CANMET usually processes 5,000 BPD of visbreaking residue in
mechanical details. The final product contains approximately 25% Petro-Canada refinery in Montreal. Petro-Canada reports that the
of non-converted residual and can be commercialized as upgraded unit is started-up when operation is economically justified and
or reprocessed crude for deep conversion units handling DC, VB or suspended when a more attractive option for processing the mix-
SDA [43,44]. ture visbreaking bottom/vacuum residue is available [40].
Three specific H-Oil processes are now promoted: In the early-2000s UOP evaluated several options focused on
providing a commercially-feasible slurry hydrocracking technol-
H-Oil/HCC: This heavy crude conversion process produces syn- ogy offering to the market. They concluded that the most efficient
crude. The objective of the unit is to enable just enough conver- approach involved Natural Resources Canada’s (NRCan) CANMET
sion to reduce viscosity and increase stability so that the Hydrocracking Process. In 2006 UOP began working with NRCan
product can be readily transported to an upgrading center. to evaluate and improve their CANMET Process technology pack-
H-Oil/DC: Difficult to treat VGOs and VGO mixtures are pro- age. Pilot plant testing as well as detailed reviews of engineering
cessed in this unit with the objective of moderate conversion. design and operations were developed before UOP acquired the
H-Oil/RC: The classical H-Oil process has been significantly exclusive worldwide rights to license the CANMET Hydrocracking
upgraded to increase conversion levels, increase product stabil- Process in 2007. Finally this work resulted in the development of
ity and reduce costs. Among the improvements made to the tra- 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 bitumen and Venezuela Zuata heavy crude oil. In 2005 it was com-
and Unionfining Process technologies [56,46]. pleted and started up a 1200 BPSD of a Commercial Demo Plant
Super oil cracking (SOC) process under development in Japan (CDP) at Eni Taranto Refinery [60]. The implementation of the first
has rather unique features, i.e. it uses horizontal furnace tubes as EST industrial plant (23,000 BPSD capacity) is in progress at Eni
the reaction zone [48,52]. A finely ground catalyst to promote Sannazzaro de’ Burgondi Refinery (Pavia, Italy) expecting to be in
cracking of the heavy feed is added to the slurry. The process em- operation by the end of 2012.
ploys severe conditions such as H2 pressure above 200 atm, tem- Headwaters Technology Innovations Group (HTIG) developed a
perature about 480 °C and relatively short residence time. So far, catalytic heavy oil upgrading technology known as HCAT. The
the process has been demonstrated using a vacuum residue on a HCAT process converts low quality feedstock such as heavy oil, res-
3500 b/d scale. idue and oil sands bitumen into high quality synthetic crude oil.
MICROCAT-RC Process was developed by ExxonMobil for hydro- The process uses a molecule sized catalyst, chemically generated
conversion of petroleum residue [57,58]. The fundamentals of this within the reactor system through a conditioning process, to
process are to add a small amount of an oil soluble and dispersible achieve high conversion of oil. HCAT significantly improves the
metal compound such as manganese or molybdenum to the reac- conversion of heavy oil as well as reduces sediment formation [61].
tor feed. At reaction conditions the additive forms a finely dis- HCAT technology offers several significant advantages over pro-
persed powder, less than 1 lm in size, which suppresses coke cesses using supported catalysts such as non-deactivating molecu-
formation. lar catalyst, constant product quality, feedstock flexibility, flexible
The process was extensively tested in bench units. EMRE used conversion (up to 95%), higher reactor throughput, simple, two-
its experience from the 250 ton/d coal liquefaction plant to develop phase gas–liquid reactor. Recently HTIG has announced that Neste
a commercial design. This unit is equivalent to about a 2000 bbl/d Oil Corporation’s Porvoo Refinery at South Jordan, Utah, is the first
residue conversion plant. refinery to commercially implement Headwater’s HCAT heavy oil
Eni Slurry Technology (EST) is a process developed in the early upgrading technology. The Neste Oil facility as a commercial refer-
1990s, after catalyst screening studies in laboratory microreactor ence would generate interest around the world in adding HCAT to
and bench scale autoclave tests [59]. Further a pilot plant with a ebullated bed upgraders. Since more than 500,000 barrels of heavy
capacity of 0.3 bbl/d was started up in 1999. Eni/Snamprogetti oil are processed in these upgraders every day, and at least
has proposed conceptual designs for the processing of Athabasca 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


3.1. Deasphalting/gasification
It is in general accepted that light low-metal content feeds are
better upgraded by RFCC, while heavy high-metal content feeds With the integrated deasphalter–gasification unit, the gasifier
by hydrogen addition or carbon rejection type of technologies. feed is taken directly from the asphalt stripper. The asphalt is
For the case of heavy and extra heavy petroleum the decision of heated to the temperature required for optimal pumping to the
using coking or hydroprocessing depends on technical and eco- gasifier prior to solvent removal, when its heat transfer character-
nomical evaluations, not only based on the production of upgraded istics are more favorable. The result is that viscosity limits on the
crude oil but also on the impact of the quality of the produced dis- asphaltenes are eliminated. Most importantly, high severity deasp-
tillates on the performance of the down-stream refining processes, halting with pentane produces a higher yield of DAO and enhances
for instance distillates from coking base upgraded oil (coker naph- the refinery’s production of diesel oil [11,17].
tha and gas oil) require further hydrotreating, while those from A summary of the feeds and products of integrated deasphalting
hydroprocessing may not need post-treatment depending on the and gasification is given in Fig. 3. Integrating solvent deasphalting
desired specification of final products. In any case, making a deci- with gasification enhances the operation and economics of both
sion on which upgrading technology is more suitable for certain technologies. The following are the main synergies between the
crude oil is not a simple task and must take into consideration sev- deasphalter and the gasifier:
eral factors, among the most important are: price of crude oil, level
of impurities of the feed, target of upgraded oil quality, and process  Beneficial use of the asphaltenes, internal consumption of low-
scheme of the refinery where the upgraded oil will be sent. level heat.
One attractive option to achieve the maximum benefit is by  Production of hydrogen for DAO treating.
combining various technologies. That is, using more than one pro-  Recovery of hydrogen from hydrotreating purge gas.
cess to upgrade heavy petroleum. In such a way the advantages of  Increase the throughput or the crude flexibility of the refinery
each approach are put together in an integrated process scheme without creating a new, highly undesirable heavy oil stream.
and this synergy may yield higher benefits than the use of single  Increases a refinery’s production of diesel oil.
processes. The most promising combinations would be derived  Increase the value of the crude because SDA removes the heavy
from solvent deasphalting, visbreaking, delayed coking, gasifica- components, reduces the metal content, reduces the Conradson
tion, hydrocracking and hydrotreating. Some of them have been al- 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  Hydrogen recovery on the order of 16,000 SCF/bbl of pitch feed.
amount of heating to recycle the solvent used in the asphaltene  Pitch gasification can be on the order of 20% lower unit capital
extraction. The heat is used to strip the solvent from the oil and cost than petcoke or coal considering elimination of the solids
the asphaltene streams so that it can be recovered and returned handling an slurry feed system.
to the process.  Pitch gasification is a ‘‘dry’’ system, therefore 20–25% lower
 The gasification process produces heat that can be used for the oxygen consumption, higher cold gas efficiency compared with
solvent recovery in the deasphalting unit. water-slurry feed.
 The energy balance between both units avoids external source  In terms of the net realization, the SDA/GF integrated process
of heat required to separate the solvent from the DAO. shows 1.33 USD/bbl crude versus 1.10 USD/bbl for SDA only,
 Minimize stripping and asphalt fired heater duties. evaluated for Canadian Cold Lake crude [67].
 The products of deasphalting and gasification can also be bene-
ficially integrated.
 The hydrogen required for HDT of DAO is a primary product of 3.2. Delayed coking/gasification
gasification and can be generated from the asphaltene to elim-
inate the need for any external supply. As in the previous combined scheme (SDA/GF), another pro-
 The purge gas from HDT may be derived to the gasifier. posal is to gasify the petroleum coke aiming at producing electric
 The sulfur in the DAO can be captured internally without power for export to electrical network and to support internal con-
increasing the load on the refinery sulfur facilities. sumption [32]. Fig. 4 shows a delayed coking–gasification scheme.
The main advantages of using a DC–GF combined scheme are:
Some other advantages may be obtained by adding TGP units to
existing solvent deasphalters. The gasification of the bottoms elim-  Heavy materials are completely exhausted to ashes and high
inates the need to blend the bottoms stream for sale because it quality sulfur.
converts the undesirable asphaltene byproduct into clean syngas  Since GF can completely destroy the feedstock, the idea of pro-
in an environmentally manner. Use of this integrated process will ducing synthetic crude appears to offer a good opportunity.
expand the market of each of these processes beyond that which  Starting from a crude it is possible to separate the heavy part
either could gain on its own. and produce electric power while the lighter part (synthetic
The main results of the integration of SDA/GF can be: 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]. 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
 Solvent introduced in the coker heater and coke drums results this scheme the pitch is fed to the DC process and further the
in highly reduced partial pressure of asphalt feed, compared coke is sent to gasification, while for the other two combinations,
with a regular delayed coking unit. 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 hydrocracking (MHDC), Permutable Reactor System (Hyvahl) and
entering to gasification. fluidized bed residue catalytic cracking (R2R).
Similarly to the concept used in FCC to represent the combined The main advantages of this integration are:
impact of certain change in operation on both gasoline octane and
gasoline yield, that is the octane barrel, for the case of heavy oil  The level of conversion to 565 °C – distillates was varied over a
upgrading the ‘‘API barrel’’ can be defined as an index to account large range throughout the catalyst cycle: from 25% at the start-
for the increase of the API gravity of the feed and the change in of-run (SOR) to 55% at the end-of-run (EOR).
the volumetric yield during reaction. With the data reported in  The 370–565 °C VGO cut is not separated from the 565 °C + vac-
Fig. 7, the results of this index are: DC–GF, 2253 API-barrel; uum residue and the entire 370 °C + cut is sent to RFCC. The
SDA–GF, 1662 API-barrel; DC–SDA–GF, 1953 API-barrel. RFCC therefore processes both hydrotreated VGO from the
From the three gasification combined schemes, the integrated MHDC unit and hydrotreated vacuum residue.
DC–GF process shows the highest API barrel index. This is sup-  The only product used as fuel is the clarified oil obtained by
ported by a high yield and higher API than the other combinations. filtration of the RFCC slurry. This can be completely con-
The SDA–GF integrations shows the lowest API barrel basically due sumed as refinery fuel, representing less than 3.5% of the
to the lowest obtained yield, even though the API is similar to the crude.
DC–SDA–GF combination.  The high flexibility and PRS system enable the refiner to pro-
duce three different kinds of fuel oil which greatly assists in
3.5. Permutable Reactor System (PRS)/RFCC combination meeting market needs for a period of at least 11 months of con-
tinuous operation on 100% VR feed. The fuels are produced by
This approach integrates the Hyvahl and R2R technologies pro- the following HDS operating modes:
cessing Arabian Light Vacuum Residue (VR). The vacuum residue (a) 100% vacuum residue, 40,000 BPSD, that produces 0.5–
desulfurization unit (VRDS) employs a combination of several cat- 0.6 wt.% sulfur feedstocks for the RFCC unit at moderate
alysts with the objective of either producing ultra-low-sulfur fuel conversion and efficient removal of metals and Conradson
oil (ULSFO) having a sulfur content of 0.3–0.5 wt.% or pretreating carbon residue.
the R2R feed, producing ‘‘zero’’ fuel oil [36]. This integrated scheme (b) 50% vacuum – 50% atmospheric residue to increase the
as shown in Fig. 8 is an example of residue upgrading via the Axens capacity to 52,000 BPSD, that performs HDS to produce
technology portfolio: high pressure hydrocracking (HP HDC), mild 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-


3.7. Ebullated bed/delayed coking
treating FCC feedstock for different residue blends.
The H-Oil process can be used in combination with a delayed
3.6. Ebullating bed combinations 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.
Two-stage in-series H-Oil plant configuration is typically a func- The mixture of distillates from straight run, H-Oil and coking are
tional combination to assure a high conversion of vacuum residue refined in fixed-bed hydrotreating units to produce synthetic crude
and good quality of the liquid products and higher HDS level be- [68].
cause of the benefits of multi-stage reactors [44]. In this configura- Advantages of this process scheme are:
tion, the first stage reactor effluent (mixed phase) is separated into
vapor and liquid products: the inter-stage liquid is fed to the sec-  Economically attractive when there is a market for the coke
ond stage reactor and the vapor is routed to the overhead of the product, however, the coker derived liquids must be further
hot high-pressure separator located after the second stage reactor. 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  Asphalt production is relatively low and can be sold or gasified
about 10 wt.% of the feed of the H-Oil unit. to produce hydrogen.
 The asphalt represents the ultimate residue which has a yield
3.8. Ebullated bed/deasphalting around the same value as with the combination of H-Oil and
Coking.
Another processing option is the combination of the H-Oil pro-  In this scheme a softening point of around 150 °C in the asphalt
cess and solvent deasphalting (SDA) as shown in Fig. 11. In this means that it can be processed in the liquid phase, either sent
scheme the H-Oil unconverted bottoms are sent to the SDA unit via pipeline to a gasification plant or to an asphalt pool.
and separated into a deasphalted oil (DAO) stream and a residual  As the DAO does not contain asphaltenes, it can be sent as a
asphalt product. The DAO can either be recycled back to the mixture with the virgin feed to the H-Oil unit.
H-Oil reactor for further conversion and/or combined with the
H-Oil derived distillates for hydrotreating [68]. The results of upgrading a heavy crude oil when an H-Oil-
The main advantages of this process scheme are: 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. post-treatment of the products from H-Oil + SDA is less severe than
An additional ebullated bed/SDA combination is to send that required for products from H-Oil + Coking, particularly for sul-
the DAO as a mixture with the virgin AR feed to the H-Oil unit. fur and CCR reduction. Table 4 shows the yield and properties of
The DAO can be deeply hydrocracked in the H-Oil unit because the H-Oil bottoms and DAO resulting from this option [68].
the DAO does not contain asphaltenes, but it has moderate resins,
aromatics and saturates. Fig. 12 illustrates this scheme. 3.9. Ebullated bed/gasification
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 The integration of H-Oil and gasification processes illustrated in
DAO conversion levels up to 90% can be obtained. The 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


a significantly different process than delayed coking, it can be inte-
For high conversion applications, and because the unconverted grated into a refinery with an existing delayed coking process. This
residue from H-Oil is not stable for use as a fuel oil blend stock, a integration would be via selective routing of each unit’s streams to
promising alternative is gasification. The main advantage of the the other unit and sharing of infrastructure and light-ends fraction-
integration of these two processes is the production of hydrogen ation systems [69].
for the H-Oil process and any downstream hydrotreating. A bal- Fig. 16 shows one possible combination of the Uniflex Process
ance conversion point is at about 83% conversion of the feed and delayed coking. In this integration, the vacuum residue is split
because there is no incentive for conversion greater than 90% as with part of it directed to the Uniflex Process and the remainder to
shown in Fig. 14 [45]. an existing delayed coking process. The Pitch from the Uniflex Pro-
Fig. 15 presents the composition of a heavy crude oil with 16.4 cess is combined with the remaining vacuum residue and directed
°API and 7.3 wt.% of sulfur, and the resulting upgraded crude with to the Delayed Coker. Heavy coker gas oil (HCGO) is now routed to
L.C. Castañeda et al. / Fuel 100 (2012) 110–127 125

FBR EBR

DC
Heavy Upgraded
SDA FBR
Crudeoil oil

GF

SPR FBR
VB

Fig. 18. Other alternatives for upgrading of heavy oils.

the Uniflex Process feed along with the Uniflex HVGO recycle be added by 2014, there would be a considerable market for the
stream. Both processes products are sent to common fractionation. HCAT technology.
The processing of vacuum residue in the Uniflex Process before
the delayed coking process accounts for the following advantages: 3.13. Other combined schemes

 Significant increases in product yields. Although not totally reported in the literature, the use of fixed-
 Reductions in net coke yield. The degree to which this occurs bed hydrotreating with some other processes, such as delayed cok-
depends on the selected conversion level in the Uniflex Process. ing, gasification, visbreaking, solvent deasphalting, ebullated-bed
 The relative economic attractiveness of the Uniflex Process ver- and slurry-bed hydrocracking, represents interesting alternatives
sus delayed coking increases with the level of conversion in the for upgrading of heavy oils. Being sediment formation one of the
Uniflex Process. main drawbacks of high pressure hydrocracking, e.g. EBR and
SPR, working FBR based technologies at moderate reaction severity
Fig. 17 shows the results of the integration of Uniflex and DC conditions will reduce this problem, thus increasing the possibility
processes in terms of the increased liquid yields of an Arab Light to combine it with other process options, as is schematically repre-
Residue. sented in Fig. 18.
The relative economic attractiveness of the Uniflex Process ver- Since asphaltenes are the main responsible for catalyst deacti-
sus delayed coking increases with the level of conversion in the vation and strongly contribute to sediment formation, it is highly
Uniflex Process. This economic advantage is maintained at lower desirable that they are either removed (by SDA) or cracked (by
conversion levels in the Uniflex Process, due to the additional pro- SPR) before the heavy oil enters the FBR hydrotreating, so that
cessing of the Pitch in the DC process resulting in some additional longer life of the catalyst is anticipated with the consequent saving
liquid yields. This then provides the opportunity to optimize the le- in catalyst replacement. Not having or having less amount of
vel of conversion in the Uniflex Process. asphaltenes in the feed to FBR will allow the hydrotreating for opti-
mizing reaction conditions to make the reaction more selective to-
3.11. Slurry-phase/fixed-bed hydrotreating wards high valuable desired products, e.g. gasoline and diesel. On
the other hand, using another process after FBR HDT has the incen-
The Uniflex Process also has synergies with a residue hydro- tive of total conversion of the residue fraction, which nowadays is
treating unit. Refiners with existing residue hydrotreating pro- the tendency towards zero fuel oil production refineries.
cesses (RHDT) have an opportunity to add a Uniflex Reactor up
front of the fixed bed reactors. This results in an integrated Uni- 4. Concluding remarks
flex-RHDT Process with the benefits of both technologies. Beside
the addition of the Uniflex Process reactor there would be the The worldwide tendency towards the production of heavy and
requirement for some additional fractionation equipment to sepa- extra-heavy crude oils represents a great incentive for exploring
rate the pitch stream from the other Uniflex products before they the possibility of combining the currently available technologies
are processed in the main RHDT reactors. The investment for this for upgrading of such crudes. Carbon rejection or hydrogen addi-
approach would be less than the cost of a delayed coking process tion based processes can work alone to reduce impurities content
[69]. and increase the API gravity of the feed. The decision of which ap-
proach is the best depends mainly on the properties of petroleum,
3.12. Slurry-phase/ebullated-bed the target regarding quality of the upgraded oil, prices of oil, and
products demand.
As previously discussed, HCAT slurry phase technology is an- Refineries like to use coking technologies, particularly delayed
other prospect to be integrated to improve the performance of coking, because it is a mature process with well-recognized com-
existing ebullated bed upgrading units as reported by Neste Oil mercial experience in spite of knowing that product yield is low-
[63]. With more than 500,000 BPD of heavy oil processed in their ered and the produced distillates require further treatment to be
upgraders and 200,000 BPD of additional estimated capacity to incorporated in the fuel pool. This way of thinking is nowadays
126 L.C. Castañeda et al. / Fuel 100 (2012) 110–127

changing as the heavy petroleum tends to produce more coke sac- [27] <http://biznews.pe/noticias-empresariales-nacionales/exxon-mobil-proveera-
unidad-flexicoking-petroperu>; Octubre 2010 [accessed 02.03.11].
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