CUP/10
ENI SLURRY TECHNOLOGY: A NEW
TECHNOLOGY FOR HEAVY OIL
UPGRADING
Alberto Delbianco a, Nicoletta Panariti b,
Mario Vito Marchionna c, Salvatore Meli a
a
Eni E&P Division, b Eni R&M Division, c Eni SpA
Via Maritano 26, 20097
San Donato Mil., ITALY
Tel. +39 02 52056120
Fax. +39 02 520 56364
Introduction
Today’s world refining industry still produces significant
amounts of petroleum by-products, such as petcoke and heavy
fuel oil whose market is shrinking. As a matter of fact, these
fuels have long been used for applications as diverse as
generating electricity and powering ships, but in the future,
even in the field of power generation, the tendency is towards
the use of more environmentally acceptable fuels (less sulfur,
less metals and possibly higher hydrogen to carbon ratio) such
as natural gas. Moreover, economic and strategic reasons are
promoting the utilization of the huge reserves of the so-called
“unconventional oil” such extra-heavy oils and bitumen from
tar sands1.
The main scopes of a conversion/upgrading technologies
are: i) to convert the atmospheric & vacuum residues into
distillates, ii) to remove poisons such as heteroatoms,
asphaltenes and metals and, iii) to increase the hydrogen
content of the upgraded materials2.
The increase of the H/C ratio can be made either rejecting
carbon or adding hydrogen. The C-rejection processes (such
as visbreaking and coking) show a very high feed flexibility
but generate low quality distillates and huge amount of by-
products3. On the contrary, the hydrocracking technologies
assure good product upgrading but the well known fixed bed
or ebullating bed technologies present severe limitations in
terms of feedstock flexibility4. As a matter of fact, supported
catalysts can be plugged by metals and coke deposits on the
porous supports.
This drawback is less significant in the case of slurry
phase hydrocracking processes because of the use of non-
supported micro-sized particles of active phase hydrogenation
1 Purge
IEA, International Energy Agency. World Energy Outlook 2004.
OECD
2
Fujita, K., Abe, S., Inoue, Y., Plantenga, P.L. and Leliveld, B., New
Development in Residue Hydroprocessing, Petroleum Tech.
Quarterly, Winter 2001-02, 51
3
Ellis, J. Paul, Tutorial: Delayed Coking Fundamentals, AIChE
1998 Spring National Meeting, New Orleans
4
Colyar, J. J., Kressmann, S., Boyer, C., Schweitzer, J.M., Viguie,
J.C., Improvement of Ebullated-Bed Technology for Upgrading
Heavy Oils, Revue de l’Institut Francais du Pétrole, 2000, Vol. 44,
397-406
catalysts. These slurry hydrocrackers employ finely dispersed
hydrogenation catalysts, such as cheap iron-based additives or
micro-sized transition metal sulphide that are usually
generated in-situ during reaction, via thermal decomposition
of oil-soluble precursors. The use of the dispersed catalysts is
very effective in preventing the coke formation assuring a
good control of the sediments precipitation and fouling, even
at relatively high conversions5.
In spite of these advantages, they have not yet made the
necessary hurdle to large-scale commercial demonstration
because of the difficulties in matching high conversion with
excellent products quality as well as due to the technological
problems connected with the catalyst handling.
In this scenario, Eni has developed a novel upgrading
process (EST: Eni Slurry Technology) which is particularly
suited for the conversion and the upgrading of a variety of
black oils material, from the conventional vacuum residues up
to extra-heavy oils (°API < 10) and bitumen.
EST Process
The simplified process scheme of the EST is represented
in Figure 1.
The heart of the process is a slurry reactor in which the
heavy feed is hydrocracked at mild conditions to produce
distillates. The hydrocracking is performed in the presence of
thousands ppm of micron-size molybdenum based catalyst
which suppresses coke formation and promotes the upgrading
reactions (sulfur, nitrogen and metals removal and CCR
reduction). The reaction product is distilled to recover the
lighter fractions (naphtha, middle distillate and VGO) while
the residue is sent to a Solvent DeAsphalting unit to extract
the upgraded DeAsphalted Oil, while the precipitated
asphaltenes as well as the catalyst are recycled back to the
reactor. The recycled asphaltenes are therefore re-dissolved in
the fresh feedstock and can be reprocessed to obtain maximum
conversion.
Distillates DAO
Feedstock &
Catalyst make-up
Hydrogen Recycling asphaltenes & Catalyst
Reactor Fractionator SDA
Figure 1. EST Simplified Process Flow Diagram.
5
Delbianco, A., Panariti, N., Marchionna, M., Upgrading Heavy Oil
Using Slurry Processing, Chemtech, November 1995, 35-43
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Feedstock Flexibility. In this way, the Eni Slurry The technical viability of the EST process has been
Technology can process heavy feedstocks assuring very high recently demonstrated running a Commercial Demonstration
conversion to distillates and DAO because does not generate Plant (CDP) of 1200 bbl/d capacity that has been realized
significant amounts of by-product, such as coke or heavy fuel inside the battery limit of the Taranto refinery (Eni R&M
oil. Division).
The validity of this process scheme has been preliminary The reaction section of the CDP plant consists of 3 slurry
demonstrated at laboratory scale and therefore using a reactors whose geometry, together with the liquid and gas
continuous pilot plant unit having a capacity of 0.3 bbl/d. In velocities, assure a high degree of back mixing in the slurry
the last four years, we have processed a variety of different phase. This is demonstrated by the axial and radial
feedstock (conventional petroleum residues, extra-heavy oil temperatures profiles that are almost isothermal.
and bitumen) and we have observed that, in all cases, the The products fractionation section comprises an
process reaches the steady-state situation, that is demonstrated atmospheric and vacuum distillation column for the recovery
by the constancy of the products distribution and product of the light, middle and heavy distillates, followed by a
quality (in terms of sulfur and nitrogen content, density and solvent deasphalting unit (SDA) working with propane. This
CCR concentration as well as by the recycle composition), last unit allows the final separation of the heaviest upgraded
with an asphaltene purge lower than 2 per cent on fresh stream (the De-Asphalted Oil, DAO), from the hydrogenation
feedstock, that is to say with a residue conversion to distillates catalyst and unconverted product that are mixed with fresh
and DAO higher than 98 per cent. The coke formation was feedstock and recycled to the reactors.
always negligible6. The first test run has been successfully completed on April
Moreover, in all cases the process assures a complete 2006 after more than 2500 hours of continuous operation with
metal removal (> 99 % HDM), an excellent CCR reduction a vacuum residue from Ural crude whose chemical
(> 95 % HDCCR), a fairly good desulphurisation and a composition is shown in Table 2.
reasonable denitrogenation (Table 1).
Table 2. Properties of the Ural Vacuum Residue.
Table 1. Comparative Performance of Different Feedstock
in Pilot Plant Experiments API CCR Sulphu Nitroge
Ni – V
Arab. Athab. gravity (wt.%) r n
Ural Zuata Maya (ppm)
Heavy Bitumen (wt.%) (wt.%)
Yield (wt. %) 7.9 17.0 3.0 0.5 75 - 244
Gas (HC + H2S) 11.5 10.9 15.1 9.9 12.9
Naphtha 5.8 4.9 14.0 3.9 4.1 The typical plant performance, that is to say the products
yield as well as the main properties of the different streams
Atm. GO 32.5 30.6 39.1 26.9 39.1 obtained during this test are summarized in Table 3. The
VGO 29.8 29.2 23.3 34.9 32.1 variability in the products distribution means that by varying
DAO (500°C+) 20.4 24.4 8.5 24.4 11.8 the operating conditions in the slurry reactor, the liquid
products slate can be partly modified according to the refinery
Upgrading specifications.
performance
Table 3. CDP Typical Products Yield and Quality from
% HDS 86 82 86 84 83
Ural Vacuum Residue
% HDM > 99 > 99 > 99 > 99 > 99
HC Atm. C3
% HDN 54 41 59 52 47 Naphtha VGO
Gas GO DAO
% HDCCR 97 97 98 96 95
Yield (wt.%) 8-11 6-10 30-35 30-35 12-20
% Conversion > 99 > 99 > 99 > 99 > 99

The Commercial Demonstration Plant (CDP Unit)

API gravity 60 41 25 23
S (wt.%) 0.03 0.2 0.6 0.8
6
Panariti, N., Delbianco, A., Montanari, R., Rosi, S., Sartori, R., The N (ppm) 50 800 2300 3000
Eni Slurry Technology Process: Development and Potential
CCR (wt.%) < 0.1 0.5
Application; ERTC 10th Annual Meeting, Vienna, November 14-16,
2005 Ni-V (ppm) <1 <1

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Conclusions
The EST process may represent a breakthrough in the
field of slurry process technologies because of its original
catalyst handling and appears as an attractive alternative
option in the state of the art technologies, since it allows
complete feedstock conversion and excellent upgrading
together with high feedstock flexibility.
The technical viability of the this new hydroconversion
process has been successfully demonstrated running a
Commercial Demonstration Plant (CDP) of 1200 bbl/d.
capacity.

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