Resid Conversion Through the Aquaconversion Technology

An Economical and Environmental Solution

R. Marzin, P. Pereira, L. Zacarias, and L. Rivas, PDVSA-INTEVEP, Los Teques,
Venezuela; Michael McGrath, Foster Wheeler, Clinton, New Jersey, USA; and
Gregory J. Thompson, UOP, Des Plaines, Illinois, USA
Abstract

INTEVEPs Aquaconversion technology features a mild residue

hydrogenation/cracking process that is achieved by a
unique catalyst activated transfer of hydrogen from water
present in the process to the residual oil being thermally
cracked.
The operating conditions are such that it will be an economically
attractive process for many refiners. The application of this technology in
refinery allows an increase in conversion level as well as in fuel gain above
those normally achieved in similar processes such as thermal cracking or
visbreaking units that are characterized by their low capital and
investment costs. The absence of any solid by-product such as
coke will be another significant advantage of the technology for many refiners.
This novel concept has been fully demonstrated in large scale pilot plants. The
process itself, has also been confirmed at the commercial scale during short test
runs in a full-size visbreaker. An immediate economically advantageous area of
application of the technology is the upgrading of H/XH crudes, to produce a
synthetic crude meeting transport and stability specifications.
A project for upgrading 100,000 BPD of an extra-heavy Venezuelan crude from
915API utilizing this technology is now under planning by a PDVSA affiliate.
The simplicity of the process and the absence of any solid byproduct will allow
this grassroots upgrade to be located in or nearby to the production field,
substantially reducing the requirements for diluent transport.
Economics for the AquaconversionTM based integrated production-upgrading
plant show a clear advantage of this technology over coking to produce
transportable heavy syncrudes.
This paper reviews the process features and demonstration
steps as well as the ongoing applications of the technology
and its economic competitiveness.
Introduction
The rush for heavy and extraheavy (H/XH) oil has already started in Venezuela.
Multinational oil companies are pledging nearly $17 billion along with Petroleos
de Venezuela PDVSA) to develop Venezuelas vast Orinoco reserves.

These companies are looking at these projects as a way to secure their crude
supply. Another attraction is that Venezuela is right on the doorstep of the United
States, which is a huge market for crude oil. The reasons for this recent interest
in heavy oil are the improvements in production and upgrading
technologies as well as attractive fiscal incentives that have been offered by the
Venezuelan government. If oil companies can make these projects pay, the
implications for world supply are significant because of the huge reserves in the
Orinoco Belt.
Within PDVSA, technology has been recognized from the early days as the only
way to significantly reduce production and upgrading costs of these H/XH
crudes and economically convert them into high-quality fuels for the growing
energy market. PDVSA-Intevep, the technological arm of PDVSA,
has devoted significant resources since the early 1970s to
answer this technology need. Today, a new thermal catalytic
steam conversion technology called Aquaconversion process
is now available as a competitive alternative to traditional
upgrading routes. This process allows the H/XH crude oil of 9
API to be upgraded to a syncrude of 15 API. This syncrude
can be transported without the need for diluent and processed
to final fuels in conventional refineries. Although the conventional
delayed coking technology has been selected in the four
projects for the Orinoco Belt already approved by the Venezuelan
Congress, this new technology is seriously being considered
for the new projects that are in the conceptual stage. This
paper describes the Aquaconversion technology and its economics
compared with alternative upgrading routes.
Technologies for H/XH Crudes
Upgrading
The countries with the largest resources in H/XH crudes are Canada, Russia,
and Venezuela. Current world reserves of H/XH crudes and bitumen are
estimated to be about 1,000 billion barrels (proven + potential recovery), and
these three countries have more than 80% of these reserves. Venezuela
concentrates most of its heavy oil and bitumen in the Orinoco 2
Belt in the eastern part of the country. Stretching 800 km from east to west and
200 km from north to south, this area represents the largest accumulation of
heavy crude in the world (Figure 1). Back in the late 1970s, PDVSA made a
huge effort to quantify the in-place reserves, which were estimated at 1.2
trillion barrels. 1

Recoverable reserves were estimated at 267 billions barrels. At an aggressive

exploitation rate of 1 million barrels per day, these reserves would represent
more than 700 years of production.
Several international companies have shown an interest in investing in
Venezuela for the production and upgrading of these H/XH crude reserves. Their
main interest is to secure a reliable source of oil supply at a minimum cost per
barrel. To date, four strategic associations among PDVSA and other
companies have been approved by the Venezuelan Congress
(Table 1), and others are at the conceptual stage. Several technologies
have been considered within these approved projects,
but the final decision in all four cases was to use delayed coking
technology. With the existing delayed coking in national
and international refineries and these new projects in the
Orinoco Belt, PDVSA will become the leader in this technology
on an installed capacity basis (about 15% of the world
petroleum coke market). These four upgrading plants will be
built at Jose in eastern Venezuela in what is called the Condominium
because the different projects will share some offsites
and utilities. A typical block diagram is shown in Figure
2. A more complete description of these projects can be found
elsewhere.
2
More advanced technologies are being considered for the
other projects being conceptualized. BP is looking at the ebullated
bed technology from IFP and Lummus; the emphasis is
on a lower-pressure level and optimized catalyst consumption
to improve the economics of such a route. Exxon is bringing
in its own Flexcor-T technology, which can be described as a
low-severity visbreaking that reduces H/XH crude acidity,
slightly improves crude API and viscosity, and maintains syncrude
stability. Coastal has been looking at visbreaking as an
upgrading route. In these associations, the PDVSA share of
the investment will be significant, and because of limited
resources, further projects will be considered only on the basis
of originality while maintaining the same level of economical
attractiveness. This approach opens the door to what has been
referred to as a beauty contest. In such a contest, delayed
coking could be at a disadvantage. However, the novel Aquaconversion
technology, developed by PDVSA-Intevep, is
entering this beauty contest as a favorite, and the following

sections describe its concept and advantages.

The Aquaconversion Process
The main strategy in the conceptualizing of the Aquaconversion
process as an option for H/XH crude upgrading is to use a
conversion process severity that is just sufficient to transform
these heavy crudes into transportable and marketable stable
syncrude and still maintain investment and operating costs at
minimum levels. Thus, further conversion will have to be done
abroad in the clients refinery using existing capacity. Additional
investment in this refinery may have to be considered. A
comparison of grassroots investment in Venezuela and additional
investment in existing refineries abroad clearly favors
the latter, and as a result, the concept of doing just the necessary
amount of upgrading in Venezuela should be more economically
attractive.
Coke handling and shipping requirements have forced the
existing projects to move to Jose and as a result the transportation
of diluent over more than 250 Km between the production site and the upgrader
is required.
An important aspect of the Aquaconversion technology is that it does not
produce any solid by-product such as coke, nor does it require any hydrogen
source or high-pressure equipment. Consequently, Aquaconversion
can be located in the production area, and thus the need for external diluent and
its transport over large distances is eliminated. As can be seen on the process
scheme shown of Figure 3, the natural light distillates from the raw crude can be
used as diluent for both the production and desalting processes.
The restrictions on the diluent API gravity and viscosity
can therefore be relaxed because of the shorter distances
associated with the upgrader field location.
The process:
The Aquaconversion technology is a catalytic visbreaking process which
operates in the presence of steam. The visbreaking technology is limited in
conversin level because of the stability of the resulting product. Because
one process requirement is that the syncrude has to be stable, standard
visbreaking allows only a 2 API upgrading of the heavy crude and only a limited

viscosity reduction, which does not ensure its transport without external diluent.
The Aquaconversion process pushes this maximum conversion
level within the stability specification by adding a homogeneous
catalyst in the presence of steam. This novel catalytic system allows hydrogen
from the water to be transferred to the resid when operated at the conditions
normally used for the visbreaking process. Similar operating conditions
(pressure and temperature) are used. This hydrogen incorporation is much
lower than that obtained when using a deep hydroconversion process under
high hydrogen partial pressure. Nevertheless, it is high enough to saturate
the free radicals, formed within the thermal process, that would normally lead to
polymerization reactions that form large asphaltenes and cause stability
problems. With this hydrogen incorporation, a higher conversion level can be
reached, thus enabling higher API and viscosity improvements to be achieved
while maintaining product stability.The Aquaconversion reaction mechanism is
shown in Figure 4.
(1) R-Rn
R. + Rn.
THERMAL CRACKING
(2) H2O
2 H. + O.
O-H BONDS DISSOCIATION
(3) R., R n. + 2 H. R-H, R n-H
FREE RADICAL H-SATURATION
(4) Rn.+ 2 O.
Rn-1 + CO 2 +H2
CARBON OXIDATION
(5) Rn., R.
Rn-Rn , R-R
CONDENSATION
cat.
cat.
cat.
The catalyst precursor is dispersed in the feedstock by
reaction with its polar components. The polar nature of the
resulting mixture allows the catalyst to migrate toward the
feedstocks more-aromatic, multiring components. The catalyst,
which is produced and activated by heat in the presence
of water, then catalyzes the dissociation of water into hydrogen
and oxygen radicals. As thermal cleavage of the carboncarbon
bonds progresses, hydrocarbon free-radicals would 3
begin to be formed. Unlike the typical visbreaking reaction
sequence, where these materials polymerize to eventually
form asphaltenes, the Aquaconversion reaction mechanism
reduces the tendency for polymerization by promoting the
addition of hydrogen radicals to the hydrocarbon free-radical.
This catalyst also accomplishes dealkylation of the alkyl aromatic
structures to form smaller aromatics, hydrogen, and carbon

dioxide. In addition, oxygen radicals from water saturate

some hydrocarbon free radicals to form carbon oxides, mostly
carbon dioxide because the thermodynamic equilibrium
favors its formation at the Aquaconversion temperature. This
entire reaction sequence can effectively terminate several
undesirable asphaltene polymerization reactions, and results
in a catalytic steam visbroken product with lower asphaltene
content than conventional visbreaking.
Process development:
The main stages in the development of the process are shown in Figure 5.
Initial studies at bench scale initiated in early 1990s, focused on catalyst and
chemistry evaluation. The process was then evaluated in a
continuous 1 BPD pilot plant at PDVSA-Intevep to assess its
performance using different feedstocks and operating conditions.
Feedstock from refineries as well as H/XH crudes from
the Orinoco Belt were tested in this small unit. The next stage
was the testing at commercial scale, which was performed in
an existing visbreaking unit of 18,000 BPD capacity in the
Isla refinery at Curacao. To adapt this unit to the Aquaconversion
scheme, a catalyst preparation skid was designed and
built by PDVSA-INTEVEP and connected to the visbreaking
plant. Two tests were performed in this unit in 1996 and 1997.
Although some constraints specific to the unit did not allow
the process to reach its full potential, most of the process
advantages obtained at the pilot plant level were reproduced at
commercial scale. Additional adaptation of the unit is required
to maintain commercial operation for a long period.
An existing 10 BPD pilot plant available at PDVSAINTEVEP
was then adapted to the Aquaconversion scheme
and is now being used to evaluate and optimize the processing
of H/XH crudes and to support engineering designs that are
being carried out by companies interested in the technology.
Several conceptual engineering studies are now being conducted
to determine both investment and operating costs of
the Aquaconversion process compared with other technologies.

AQUACONVERSION PERFORMANCE
WITH H/XH CRUDES
As an example of the capability of the Aquaconversion process,
its performance with the Pilon crude is described in the
following section. Pilon is a 14 API blend consisting of a mixture
of heavy crudes, such as Morichal or Cerro Negro, and a
diluent. Its atmospheric resid is therefore representative of the
Orinoco Belt resids, and its characteristics are shown in Table 2.
This resid was fed in the Aquaconversion 10 BPD pilot
plant at PDVSA-INTEVEP and processed at different severity
levels. The severity level was controlled through the soaker
temperature, and its effect on product quality was monitored
principally in terms of stability through the P-value and resulting
syncrude API and viscosity. The results can be seen in Figures
68. As severity is increased, a slow decrease in the Pvalue
can be observed, but it allows for a significant increase
in the syncrude API of 5 and similarly a drastic reduction in
the syncrude viscosity of 99% at 50C, which allows economical
transportation. The improvement relative to visbreaking
can be derived from these same graphs through the difference
in syncrude API and viscosity between 20% (visbreaking) and
40% (Aquaconversion process) 500C + conversion levels.
Figure 9
shows the general mass balance of the Aquaconversion
flow scheme derived from the same pilot plant test run
with Pilon. Important parameters of the Aquaconversion performance
are shown in Table 3. The most relevant are the positive
asphaltene and carbon conversions that are far superior to
the negative conversions typical of visbreaking even at lower
severity.
These parameters influence the product yield to be
obtained when the syncrude is processed in the client refinery,
where the resid will most probably be processed in a coker.
The overall coke yield obtained when the resid is first processed
in the Aquaconversion process before being fed in a
coker is lower than the yield from a single one stage full conversion
coker.
Aquaconversion Economics
To assess the economics of the Aquaconversion route, a comparative

economical evaluation was performed for a typical

Orinoco Belt project. Three cases were selected:
Aquaconversion process,
Delayed coking, and
Dilution.
For the delayed coking case, the upgrader was located at Jose because
existing projects based on this technology to date have chosen that
location. For the Aquaconversion case, the upgrader was
located in the field because of the advantages specific to the
technology. The three cases are shown in Figure 10. For the
economical evaluation, the integrated production-upgrading
scope was selected to fully present the attractiveness of the
project. The results shown in Figure 10 indicate that the Aquaconversion
scheme is competitive with the traditional coking
route.
Based on the attractiveness of the Aquaconversion route,
PDVSA-FAJA, which is the new organization of PDVSA
looking at all the Orinoco projects, is including Aquaconversion
as an alternative for the new projects in the conceptual
stage. Several international potential partners for these
projects have signed secrecy agreement with the technology
licensors (UOP, Foster Wheeler, and Intevep) to fully evaluate
this new route.
4
Conclusion
PDVSA-INTEVEP has developed a new upgrading technology
that is competitive with the traditional delayed coking
route. This technology has been tested extensively at pilot
plant level and at commercial scale in an existing 18,000 BPD
visbreaker unit. The economics are attractive because the process
uses a plant configuration similar to visbreaking with its
low pressure and temperature design parameters. The process
allows the 9 API H/XH crude to be upgraded to a stable 15
API syncrude with reduced bottoms that can be transported
without the need for diluent. Immediate plans are to adapt an
existing commercial visbreaking plant to the Aquaconversion
mode to fully demonstrate the technology in long term operation.
A syncrude shipment will be prepared from Orinoco H/
XH crudes in this unit and tested in U.S. refineries to get an

early assessment of its performance in a client refinery. Several

international partners interested in joint ventures with
PDVSA to secure their crude supply are now looking seriously
at this new upgrading route. This new technological element
within the H/XH business could boost the exploitation of
the huge existing reserves.
References
1. Tedeshi, M., Reserves and Production of Heavy Crude
Oil and Natural Bitumen, 13
th
WPC, Topic 13, Buenos
Aires, Oct. 1991.
2. Solari, R.B., Marzin, R., and Soler, L., Integration of
Upgrading in the Production of Extraheavy Crudes from
the Orinoco Belt. 5
th
World Congress of Chemical Engineers,
Paper 84c, San Diego, July 1996.
3. Marzin, R., et al, The Aquaconversion Process, A new
Approach to Residue Processing, 1998 NPRA Annual
Meeting, San Francisco, March 1998.

Diluted
Pilon
Crude
API gravity
Sulfur, wt%
C7 Asphaltene, wt
%
Conradson
carbon,
wt% Viscosity, cSt
@ 60C

13.0
2.98
9.09
11.3

1498

350C+
Resid
7.1
3.65
13.4
15.2

782

@ 100C @ 135C TAN, mg KOH/g

Vanadium, wt
ppm
Nickel, wt ppm

152
3.5
271
37

2.5
449
112

Diluted Pilon Crude and Resid Characteristics