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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

INTEVEP’s 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
9–15°API 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 Venezuela’s vast Orinoco reserves.

and these three countries have more than 80% of these reserves. a new thermal catalytic steam conversion technology called Aquaconversion™ process is now available as a competitive alternative to traditional upgrading routes. and Venezuela. the implications for world supply are significant because of the huge reserves in the Orinoco Belt. Stretching 800 km from east to west and 200 km from north to south. 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.000 billion barrels (proven + potential recovery). 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. Back in the late 1970s. Within PDVSA. has devoted significant resources since the early 1970s to answer this technology need. Technologies for H/XH Crudes Upgrading The countries with the largest resources in H/XH crudes are Canada. this new technology is seriously being considered for the new projects that are in the conceptual stage. PDVSA made a huge effort to quantify the in-place reserves. PDVSA-Intevep. which were estimated at 1. This paper describes the Aquaconversion technology and its economics compared with alternative upgrading routes. Today. 1 . Russia. this area represents the largest accumulation of heavy crude in the world (Figure 1). which is a huge market for crude oil. Another attraction is that Venezuela is right on the doorstep of the United States. This process allows the H/XH crude oil of 9 API to be upgraded to a syncrude of 15 API.2 trillion barrels. If oil companies can make these projects pay. Current world reserves of H/XH crudes and bitumen are estimated to be about 1.These companies are looking at these projects as a way to secure their crude supply. 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. the technological arm of PDVSA. Venezuela concentrates most of its heavy oil and bitumen in the Orinoco 2 Belt in the eastern part of the country.

Coastal has been looking at visbreaking as an upgrading route. and the following . developed by PDVSA-Intevep. To date. four strategic associations among PDVSA and other companies have been approved by the Venezuelan Congress (Table 1). However. the novel Aquaconversion technology. and because of limited resources. which can be described as a low-severity visbreaking that reduces H/XH crude acidity. With the existing delayed coking in national and international refineries and these new projects in the Orinoco Belt. A typical block diagram is shown in Figure 2. further projects will be considered only on the basis of originality while maintaining the same level of economical attractiveness. but the final decision in all four cases was to use delayed coking technology. A more complete description of these projects can be found elsewhere. 2 More advanced technologies are being considered for the other projects being conceptualized. is entering this “beauty contest” as a favorite.Recoverable reserves were estimated at 267 billions barrels. Several technologies have been considered within these approved projects. delayed coking could be at a disadvantage. BP is looking at the ebullated bed technology from IFP and Lummus. This approach opens the door to what has been referred to as a “beauty contest.” In such a contest. the PDVSA share of the investment will be significant. Several international companies have shown an interest in investing in Venezuela for the production and upgrading of these H/XH crude reserves. and others are at the conceptual stage. 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. these reserves would represent more than 700 years of production. At an aggressive exploitation rate of 1 million barrels per day. and maintains syncrude stability. slightly improves crude API and viscosity. 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. Their main interest is to secure a reliable source of oil supply at a minimum cost per barrel. In these associations.

An important aspect of the Aquaconversion technology is that it does not produce any solid by-product such as coke. standard visbreaking allows only a 2 API upgrading of the heavy crude and only a limited . The visbreaking technology is limited in conversión level because of the stability of the resulting product. A comparison of grassroots investment in Venezuela and additional investment in existing refineries abroad clearly favors the latter. The restrictions on the diluent API gravity and viscosity can therefore be relaxed because of the shorter distances associated with the upgrader field location. Consequently. The process: The Aquaconversion technology is a catalytic visbreaking process which operates in the presence of steam.sections describe its concept and advantages. As can be seen on the process scheme shown of Figure 3. 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. Additional investment in this refinery may have to be considered. the natural light distillates from the raw crude can be used as diluent for both the production and desalting processes. further conversion will have to be done abroad in the client’s refinery using existing capacity. nor does it require any hydrogen source or high-pressure equipment. 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. and thus the need for external diluent and its transport over large distances is eliminated. Aquaconversion can be located in the production area. Thus. Because one process requirement is that the syncrude has to be stable. and as a result.

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

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

such as Morichal or Cerro Negro. where the resid will most probably be processed in a coker. The results can be seen in Figures 6–8. The severity level was controlled through the soaker temperature. 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 50°C. Aquaconversion Economics To assess the economics of the Aquaconversion route. its performance with the Pilon crude is described in the following section. 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) 500°C + conversion levels. 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. and its effect on product quality was monitored principally in terms of stability through the P-value and resulting syncrude API and viscosity. and a diluent. Important parameters of the Aquaconversion performance are shown in Table 3. and its characteristics are shown in Table 2. As severity is increased. Pilon is a 14 API blend consisting of a mixture of heavy crudes. 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. This resid was fed in the Aquaconversion 10 BPD pilot plant at PDVSA-INTEVEP and processed at different severity levels. Its atmospheric resid is therefore representative of the Orinoco Belt resids. Figure 9 shows the general mass balance of the Aquaconversion flow scheme derived from the same pilot plant test run with Pilon. a slow decrease in the Pvalue can be observed. These parameters influence the product yield to be obtained when the syncrude is processed in the client refinery. a comparative . which allows economical transportation.AQUACONVERSION PERFORMANCE WITH H/XH CRUDES As an example of the capability of the Aquaconversion process.

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. For the economical evaluation. Three cases were selected: Aquaconversion process. The economics are attractive because the process uses a plant configuration similar to visbreaking with its low pressure and temperature design parameters. Several international potential partners for these projects have signed secrecy agreement with the technology licensors (UOP. and Dilution.000 BPD visbreaker unit. A syncrude shipment will be prepared from Orinoco H/ XH crudes in this unit and tested in U. 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. 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.economical evaluation was performed for a typical Orinoco Belt project. the upgrader was located at Jose because existing projects based on this technology to date have chosen that location. is including Aquaconversion as an alternative for the new projects in the conceptual stage. The three cases are shown in Figure 10. Foster Wheeler.S. refineries to get an . For the delayed coking case. PDVSA-FAJA. For the Aquaconversion case. the integrated production-upgrading scope was selected to fully present the attractiveness of the project. Immediate plans are to adapt an existing commercial visbreaking plant to the Aquaconversion mode to fully demonstrate the technology in long term operation. which is the new organization of PDVSA looking at all the Orinoco projects. and Intevep) to fully evaluate this new route. the upgrader was located in the field because of the advantages specific to the technology. Delayed coking.

San Diego. R.65 13. 1998 NPRA Annual Meeting.98 9. Tedeshi.B.2 . Marzin. This new technological element within the H/XH business could boost the exploitation of the huge existing reserves. Paper 84c. wt% C7 Asphaltene.. Reserves and Production of Heavy Crude Oil and Natural Bitumen..0 2. L. Marzin. Topic 13. 5 th World Congress of Chemical Engineers. A new Approach to Residue Processing. wt% Viscosity. 3. M. San Francisco. 2. wt % Conradson carbon. 13 th WPC. Buenos Aires. et al. Solari. Integration of Upgrading in the Production of Extraheavy Crudes from the Orinoco Belt. March 1998. July 1996. cSt @ 60C 13..4 15.09 11.1 3. 1991. References 1.early assessment of its performance in a client refinery. Oct.. R. R..3 1498 350C+ Resid 7. Several international partners interested in joint ventures with PDVSA to secure their crude supply are now looking seriously at this new upgrading route. The Aquaconversion Process. and Soler. Diluted Pilon Crude API gravity Sulfur.

mg KOH/g Vanadium. wt ppm Nickel.5 271 37 2. wt ppm 152 3.782 @ 100C @ 135C TAN.5 449 112 Diluted Pilon Crude and Resid Characteristics .