Novel Fluid Catalytic Cracking Technology excellence in heavy feedstock processing

Luiz Fernando Leite, Jos Mozart Fusco, Jos Geraldo Ramos, Jorivaldo Medeiros, Petrobras R&D Center Marcelo Andr Torem, Fabrica Carioca de Catalisadores S/A Brazil Abstract
Fluid Catalytic Cracking is renowned as the most complex and profitable process in the refining industry, being continuously upgraded since its dawn, in 1942. PETROBRAS Advanced Converter PACRC- has been developed aiming to process atmospheric residue from Brazilian crude, which has 10% wt CCR, high asphaltene and nitrogen compounds content. This technology encompasses a set of proprietary technological developments as: A closed cyclone system, named PASS technology, to allow a quick separation between cracking products and catalyst, which also provides its pre-stripping; An optimized feedstock injection system, called ULTRAMIST, operating at supersonic speed with low pressure drop and a better usage of vapor energy in the oil atomization; Improvements in riser; Optimization of equipment mechanical design. FCC environmental problems and on going technologies focused on impact mitigation are discussed. It is also reported an example within the refining area of the supply chain integration, in which PETROBRAS and Fabrica Carioca de Catalisadores, a catalyst supplier, strive for synergistic solutions that resulted in the following developments: A special catalyst system, focused on improving the accessibility to larger molecules, with minimum penalties in catalyst attrition properties, resulting in better bottoms conversion and coke selectivity; Optimization of metal passivation function for a better scavenger activity; The use of flushing catalyst, cascading low metal content equilibrium catalyst for reducing the global fresh catalyst make-up. Commercial data from the two new PETROBRAS RFCC Units are reported: Capuava Refinery (RECAP), 19,000 bpd, in So Paulo State, and Landulpho Alves Refinery (RLAM), 63,000 bpd, in Bahia State. Although these refineries are processing refractory feedstocks, they are providing conversion and yields to noble products similar to those obtained with more conventional feedstock. A third unit designed with the same technology at Alberto Pasqualini Refinery (REFAP) is presently under EPC phase.

Introduction Brazilian Oil Scenario

The petroleum scenario in Brazil indicates a higher availability of domestic crudes, due to large investments in oil production projects, mostly in the Campos basin area. By 2005, PETROB RAS will be producing 1.9 million bpd, which will be close to the Brazilian oil demand at that time. The domestic crude is heavier than the normal imported one, resulting in a higher yield of vacuum residue, about 30 32% wt. It is a sweet crude but contains more nitrogen compounds and the naphthenic acidity level is high.

The market globalization, which spurs competitiveness in the oil industry and the worldwide depressed fuel oil market stimulate the maximum conversion of residual streams, aiming at improving the refining margin. Natural gas consumption is increasing fast in Brazil, due to a much higher availability, as a consequence of importation from Bolivia and a higher internal production of associated gas. Accordingly, there is a surplus of fuel oil in our market owing to its displacement by natural gas. PETROBRAS in particular has the additional challenge of matching the increasing supply of Brazilian oil with the need of producing diesel and gasoline with a more stringent specification concerning quality and environmental aspects.

PETROBRAS FCC Expertise

Although the FCC process was originally developed in 1942, it is a technology that has been evolving continuously and was an extraordinary ability to be adapted to the refining market demands. The PETROBRAS background in this area of knowledge encompasses revamps of eleven FCC units, three grass roots RFCC projects and the capability of selecting, formulating and manufacturing tailormade catalyst. PETROBRAS has processed, in some refineries, feedstock with vacuum residue content up to 20% volume and Conradson carbon residue over 2% wt, in its conventional FCC units, since the end of the eighties. Due to the good output of residue processing program, the company decided to go one step further and devoted considerable resources in its R&D organization to develop a new RFCC technology, using a vast array of tools such as lab-scale, pilot and prototype units, as well as process simulators. The Strategic Refining Technology Program was created in 1994 to tackle the technological demands for processing heavier domestic crude(1). In FCC area the challenge was to process 100% atmospheric residues from Campos basin crudes. Consequently, the PAC RC ( PETROBRAS Advanced Converter) technology came up and was applied in three new FCC units for residue processing.

Residue Fluid Catalytic Cracking

The RFCC process consists of the same steps of the conventional process. However, due to the nature of the residue, with a higher content of high boiling point hydrocarbons and coke precursors, as well as high level of contaminants in the feedstock, special attention must be paid in order to minimize coke and fuel gas formation, via process and catalyst optimization. Thus, some aspects concerning the solutions developed at PETROBRAS for the processing of residues are presented and discussed as well as their application to the PAC RC converter of RECAP(2) and RLAM. The technologies employed and their critical aspects are described below: UltraMistTM Feed Nozzle and catalyst pre-acceleration system, aiming at ensuring high efficiency in the contact between the feedstock and the catalyst; Reactional system for optimizing the catalytic cracking in the Riser; Advanced Separation System PASS R Technology with a high spent catalyst stripping efficiency; Regenerator allowing minimum deactivation of the catalyst and low content of coke in the regenerated catalyst; Selection of high performance catalytic system; Environment impact mitigation. Most of these innovations and PETROBRAS expertise in process design are included in our FCC simulator and optimizer, which is named SimCraq OT. This tool is being used by the R&D, the Basic Engineering group, as well as by the operational teams in our refining complex.

Feed Nozzle and Riser

The region where the feedstock is introduced into the Riser is highly complex and undergoes various simultaneous physical and chemical processes. The atomized feedstock contacts the hot catalyst undergoing vaporization. The catalyst is cooled down due to simultaneous processes of vaporization and catalytic reaction of the hydrocarbons in the vapor phase. The way to maximize the catalytic conversion, thereby minimizing thermal cracking reactions, is to combine rapid feedstock vaporization with the simultaneous minimization of hot points. Hence, the key elements that optimize effective contact between the feedstock and catalyst are: Dispersion of hydrocarbon feedstock into small droplets, approximately the size of the catalyst particles; Atomized feedstock with high penetration providing complete coverage of the entire riser cross section; Turbulent flow regime of the regenerated catalyst. In 1980, concurrently with the beginning of processing in conventional FCC units of gasoil feedstocks with the addition of residue, PETROBRAS initiated studies for development and improvement of the feed nozzle. With the evolution of models, in addition to commercial scale tests, bench tests were performed for measuring the size of droplets, the shape of the jet, distribution of liquid, quantity of movement, pressure drop, etc. Owing to the success presented by following generations of these nozzles, the obtained gains encouraged new developments. The 6th generation UltraMistTM feed nozzle has been recently designed and is considered the state of the art in the FCC feedstock atomization process(3). UltraMistTM uses water vapor energy in supersonic flow to promote an efficient atomization and generate an extremely fine mist, with high penetration in fan-like shape. These characteristics are of utmost importance for residue cracking, where the contact between the feedstock and catalyst is more critical, due to the existence of 20 to 40% of very heavy hydrocarbons, in the liquid state, under the operating conditions of the Riser base. RECAP converter design has contemplated the use of eight nozzles arranged in an alternate pattern in two elevations, with four nozzles each, as illustrated in Figure 1. At RLAM converter, twelve UltraMist feed nozzles were installed. In the initial pre-acceleration section of the Riser, the correct definition of the number of nozzles, geometry and distribution of preacceleration vapor are key elements in establishing a homogeneous and stable vertical flow, in turbulent flow regi me, for an effective feedstock-to-catalyst contact in the section where feedstock is introduced. Tests were done in an industrial riser using the tomographic technique, which demonstrated the importance of maintaining the requirements mentioned above for achieving a good catalyst flow profile. In order to maintain the flux near plug flow, the PETROBRAS Riser sizing designs lead to operations in a higher speed range, with the contact time being determined according to the feed characteristics. In addition to the contact time and speed profile of the Riser, the partial pressure of hydrocarbons is also important in determining coke and fuel gas selectivity in residue catalytic cracking. Thus, the range of allowable pressures at the riser base is set beforehand, according to the feedstock properties, with an eye on promoting the minimum partial pressure of hydrocarbons.

PETROBRAS Advanced Separation System PASSTM

A more selective cracking in the Riser, resulting from the improvement of the feedstock-catalyst contact systems combined with the use of high activity and selectivity catalysts led to the need for efficient systems for separating products from spent catalyst, in order to reduce or even eliminate over-cracking reactions. The PETROBRAS Advanced Separation System PASSTM is an innovative technology of unsealed closed cyclones. The cyclone directly coupled to the Riser has the bottom catalyst discharge end

open to the diluted phase of the Separation Vessel and does not have a dip leg. Besides ensuring simplicity and operational stability, it presents an advantage over confined and sealed systems which is the capacity to minimize entrainment of hydrocarbons into the Stripper (4). Measurements with radioactive tracers in units equipped with the PASS TM system have shown that the passage of hydrocarbons to the Stripper is minimal. The catalyst collected in the cyclone coupled to the Riser is discharged into the diluted phase of the Separation Vessel, in a steam rich environment, providing an extra stripping of the catalyst. The units equipped with the PASSTM system began operating with a significantly reduced hydrogen/coke ratio, in the range of 4.5 to 5.5 wt %. Due to the high heating value of hydrogen burning, about four times greater than the heat for burning carbon monoxide to form carbon dioxide, the passage of hydrocarbons not recovered from the stripper to the regenerator considerably increases the amount of energy released by burning coke in the regenerator and, as a result, increases the thermal load of the Catalyst Cooler in the case of residue cracking units. In spite of the significant reduction in the importance of the Stripper in units equipped with the PASS TM system in normal operation, the former still continues to be an essential equipment to minimize the entrainment of hydrocarbons into the Regenerator during the occurrence of abnormal conditions during operation, such as pressure surges, sudden interruption of vapor, etc. An additional advantage of PASS TM system is the absence of contact between cyclone with Stripper catalyst bed, so level oscillation does not affect the cyclone performance and the catalyst level control is not required.

Regenerator and Heat Removal System

The Regenerator plays an important role in the fluid catalytic cracking process and its design must meet the following three objectives: Recover the activity of the spent catalyst by burning the coke deposited during cracking reactions, Generate heat to cater to the needs of endothermic processes in the Riser, preserve the integrity of the catalyst by maintaining its activity and selectivity. Due to environmental restrictions, it is also necessary to minimize the particulates emission through the use of high efficiency systems, such as the cyclones currently designed by PETROBRAS. The intrinsic characteristic of residue cracking is to produce a higher coke yield. Consequently, the amount of energy provided by its burning is greater than that needed for meeting the thermal demands of the Riser and making up for losses to the environment, resulting in a drastic temperature increase of Regenerator dense phase and all disadvantages arising there from, if a system, for heating removal from the Regenerator, such as a Catalyst Cooler, is not applied. The regeneration s ystems accounts for 60 to 80% of the total investment of the RFCC converter, depending on the coke formation trend of the residue. Therefore, the selection of its characteristics is a fundamental stage in the development of the residue cracking technology. During the development of the PETROBRAS residue converter model, several studies were carried out, aiming at the selection of the best design alternative for the Regenerator combined with the best heat removal system(5). After preliminary studies, it w observed that a Regenerator with a single as stage complied with the previous assumptions(6) and two alternative routes for the development of the regenerator design were contemplated, considering: Pneumatic transport regime or plug flow; Fast fluidized bed regime, in perfect mixing. In view of the characteristics of higher coke formation of residual streams from Campos Basin, regardless of the alternative of the type of combustion, the design would contemplate the use of a Catalyst Cooler, for the regeneration temperature to be kept within the 690 710 C range, compatible with the minimization of the deactivation of the catalyst and catalyst/oil ratio suitable for residue cracking.

The total combustion route was defined considering the advantages offered in relation to partial combustion, namely: Minimum partial pressure of water in the regenerator resulting from the low hydrogen/coke ratio provided by the efficient stripping system of the PASS TM separation system; Lower coke content in the regenerated catalyst, for the same catalyst inventory, with better utilization of the characteristics of high selectivity and accessibility of the catalytic system; Use of a sensitive heat recovery steam generator to replace the CO boiler, with a lower operating cost; Stability of regenerator operation by the ease of controlling total combustion. A study for a 7000 m3/d capacity unit was performed, considering a feedstock with Conradson carbon residue of 8.5 wt %, 10.0 wt % of coke yield and conversion of 71.0 vol. %. The best technicaleconomic alternative was a single stage, total combustion regenerator with a turbulent flow regime in perfect mixing, (5). Its simple geometry minimizes the use of internal equipment favors the use of pipe grid type air distributor, ensuring excellent coverage of the area and air/catalyst contact. Related to the Catalyst Cooler, the available licensors were contacted and a technology evaluation comparing them was carried out.

Catalytic System Design

Aiming at having a good integration of the supply chain in refining area, PETROBRAS set up a jointventure with AKZO NOBEL for FCC catalyst manufacturing, FABRICA CARIOCA DE CATALISADORES S.A (FCC S.A)., located in Santa Cruz, near Rio de Janeiro. The domain in FCC catalyst technology allows PETROBRAS to get a better tuning of process-catalyst binomial, which has been improving the commercial yields of FCC units in Brazil, via the continuous introduction of tailormade catalyst, as some examples are shown in Table 1. This experience has been frequently shared with international clients. The FCC catalyst development system is based on the joint efforts of different players: the refiner, that represents the market needs; the R&D center, implementing the refiner inputs into fast-response research projects and FCC S.A., responsible for bringing the final developed product to industrial level. This integrated system responds extremely well to the ever-changing demands of fuel and petrochemical markets, presenting superior commercial performance than state-of-the-art catalysts from traditional competitors. Table 1 Introduction of novel catalysts

Petrobras FCC Unit (year) REGAP-2 (1995) REFAP (1998) REGAP-2 (1998) REFAP (2000) REVAP (2001)

FCCS/A Catalyst (1) Vision Vision Cobra Conquest Cobra

Competitor Catalyst (2) E1 G1 G2 E2 E3

Profitability (1)-(2) (1000 US$ /year) 2,814 1,133 2,485 1,840 6,385

For an appropriate FCC catalyst to succeed in residue cracking application of Brazilian feedstocks(7) it should:

Improve diffusion of large reactant molecules to the active acid sites in order to increase bottoms cracking, i.e., conversion of residual compounds; this is specially advantageous when contact catalystfeedstock is optimized at the bottom of the riser (ULTRAMISTTM); Enhance egression of reaction products from the catalyst particles, particularly due to the reduced contact time promoted in the post riser separation devices (PASSTM Technology), thus avoiding undesired secondary reactions and overcracking; Mitigate the harmful effects of metals like nickel and vanadium in high concentration; Compensate the transitory neutralization of acid sites by basic nitrogen; Reduce the coke forming tendency of the highly polyaromatic feedstock; Preserve gasoline quality by attenuating the formation of unstable compounds. PETROBRAS and AKZO NOBEL have developed a novel FCC catalyst assembling technology that gives higher accessibility to catalyst particles, heightening the probability of large molecules reaching the functional sites (9,10). Several aspects of the FCC catalyst manufacturing and compounding have been studied at PETROBRAS R&D Center, resulting in the multi-particle system successfully applied to the commercial RFCC unit in operation (8). In order to mitigate the higher metal content in the catalyst several technological solutions were studied, such as demetallation of equilibrium catalyst (e-cat), magnetic separation of e-cat, chemical vanadium passivation by injecting liquid additives into the feed, vanadium capturing in the form of solid additives or incorporated in the catalyst and the simultaneous use of fresh catalyst and good activity and low metal e-cat. Among these alternatives, the latter, also known as flushing, was the one that achieved the best economic benefits in terms of yield profiles and fresh catalyst consumption(8). Table 2 illustrates the benefits of flushing catalyst, simulated in Microactivity Test. Table 2: Flushing Catalyst Benefits

100% Fresh Flushing catalyst Fresh catalyst consumption t/m3 feed e-cat consumption t/m3 feed e-cat vanadium ppm-wt Yields @ constant coke, relative deltas: Hydrogen wt% LPG wt% Gasoline wt% Bottoms wt% Delta coke wt% Conversion wt% 2.4 0 Base Base Base Base Base Base Base 1.6 2.0 Base 2000 17 +31 +18 43 14 +18

Intending to outperforme in residue processing, PETROBRAS opted for a multi-particle catalyst system (3,11), where different functionalities are enhanced: A particle with a larger contribution of the Y-zeolite for getting a high LPG production and moderate olefinicity in gasoline, aiming at gasoline stability; A particle with enhanced matrix acidity and extra accessibility for maximum bottoms; An low metal e-cat flushing component for reducing coke and gas and increasing the noble product yields. Such system is now in place at RFCC Units of RECAP and RLAM with outstanding performance.

Environmental Impact Mitigation

The standard refining processes are not friends with the environment, therefore many refiners have been striving to control and mitigate contamination. In the FCC area some progress has been achieved but there is still a big room for improvement. In Table 3, some technologies applied to palliate contamination are shown. Table 3 Options for Environmental Impact Mitigation

Source of Contamination

Mitigation 3rd Stage Cyclones, Scrubber, Electrostatic Precipitator, High-efficiency Cyclone, Better Catalysts Attrition Feedstock Catalysts HDT, Scrubber, Additives &

Particulates SOx, NOx CO CO2 E-Cat

Total Combustion, Combustion Promoter Better Selectivity & Conversion Cement Industry, Recycling

PETROBRAS has some achievements in this regard and is applying state-of-the-art technologies in its FCC projects. A turbo-expander and a boiler of sensitive heat were included to optimize energy recovery at RFCC Units of RECAP and RLAM. This resulted in a very substantial energy saving, making the refinery energetically independent and nowadays even able to supply neighbors with th e generated energy. Taking into consideration the environmental protection, a system of third-stage cyclones was installed both to protect the turbo-expander and to reduce particulate emissions at a level compatible with the best international practices. Cyclone optimization projects(3) are in progress at PETROBRAS R&D organization, aiming at the reduction of catalyst loss: A special dipleg sealing system was developed for the 2nd Stage Cyclone of the Regenerator Vessel. A high efficient particle collection was obtained due to minimization of gas entrance by its dipleg. Moreover a higher running time was reached as consequence of the absence of movable part devices. Particle emission was reduced to 130-150 mg/Nm3 with an average particle size of 3 m FCC Unit of Manaus Refinery; Another special sealing dipleg system was developed for the cyclone of the Separation Vessel, which is in series with the closed cyclone, reducing by one tenth the amount of particulate material that goes to the bottom of the Fractionation Tower, thus decreasing significantly the ash figures of decanted oil.

Besides optimization studies of geometric parameters of cyclones are underway at Plexiglas Pilot Unit applying Laser Doppler Velocimetry and Phase Doppler Particle Analysis technique. New catalyst and additives have been developed intending the reduction of SOx and NOx emissions. Different matrix and metals oxides have been combined and a novel catalyst system designed for reduction of aromatics, olefins and sulfur in cracked naphtha.

Novel high liquid products yield technologies

PETROBRAS R&D portfolio also includes innovations aiming at magnifying the liquid product output per CO2 generated, following the trend of complying with the Kyoto Protocol. It is worth to mention the Downflow Reactor and Feedstock Pre-vaporization technologies. The former is being presented in the congress by the paper Ultra-selective FCC process with Downflow Reactor and optimised catalyst system Pinho, A & alli.

RFCC Commercial Performance

The Capuava Refinery unit started up in December 1999, successfully processing 90% Atmospheric Residue from Albacora crude with Conradson carbon residue about 8.0, as shown in Table 5. This is a naphthenic feedstock that is much more refractory than a paraffinic one, as the blend of RN and Urucu. Anyway the conversion of 72% for a feedstock of the sort of Albacora is an excellent result(2). TABLE 5- Commercial data of Capuava Refinery

Rn (50% Vol)/ Uruc (50% Vol) API 21.4 S (%w) 0.43 CCR (%w) 6.8 Asphaltenes (%w) 2.3 Total Nitrogen (ppm) 1874 Ni (ppm) 11 V (ppm) 8 Conversion (% vol) 84.0 Dry Gas (%w) 4.4 LPG (% vol) 26.1 Gasoline (% vol) 65.8 LCO (% vol) 10.1 Decanted Oil (%vol) 5.9 Coke (% w) 9.4 Feedstock

Albacora (90% Vol) 17.2 0.63 8.0 2.0 3743 9 18 72.0 5.3 19.2 54.9 16.4 11.6 10.5

The second RFCC Unit went on stream in April 2001 at Landulfo Alves Refinery in Bahia state. Processing a blend of untreated Atmospheric Residue from Rio Grande do Norte crude, that is the major participant in the mixture, with Conradson Carbon residue ranging from 5.0 to 7.6 weight %. The unit is running quite smoothly and showing good conversions to noble products as depicted in Table 6.

TABLE 6 PAC RC Commercial data from Landulfo Alves Refinery

FEEDSTOCK RN (85% VOL) API 19.3 S (%w) 0.49 CCR (%w) 6.3 Asphaltenes (%w) 2.0 Total Nitrogen (ppm) 2730 Ni (ppm) 15 V (ppm) 8.4 Conversion (% vol) 77.6 Dry Gas (%w) 5.5 LPG (% vol) 26.3 Gasoline (% vol) 56.4 LCO (% vol) 13.1 Decanted Oil 9.3 Coke (% w) 9.2

Conclusions
The present and future refining scenario spur the maximum conversion of the residual streams, aiming at the yield of more valuable products to get a better margin and to reduce the production of heavy fuel oil, due to its depressed market. The PAC RC - PETROBRAS Advanced Converter is a good option for residue upgrading. It is a commercially proven technology that encompasses other proprietary technologies as the feed nozzle ULTRAMIST, quick separation devices as the close cyclones PASS, and one stage full combustion regenerator. It can process Atmospheric Residue of refractory feedstocks with CCR higher than 8 and high asphaltene content at a good conversion and selectivity into noble products.

Figure 1 Feedstock nozzle arrangement

Figure 2 RFCC Unit at RLAM

References
(1) Baratelli Jr., F., Assayag, M.I., Leite, L.F. Technological strategies for the optimization of the Brazilian petroleum industry, 16th WPC, Calgary, Canada, June 11-15, 2000. Fusco, J.M., Einsfeldt, M., Medeiros, J., Freire, P.S., Patrcio Jr., N., Tan, M.H., Ramos, J.G., Torem, M.A. PACRC - Um Marco no Processo de Craqueamento Cataltico Fluido, 4o Encontro SulAmericano de Craqueamento Cataltico, Manaus, Brazil, Aug. 2000. Leite, L.F. The Refining Process Technology at PETROBRAS Smart Refining Sept 3-4th,2001, TheHatton, London. Chang,T. PETROBRAS Implements $29 million Refining-technology Program, Special Edition, March 22,1999, Oil & Gas Journal. Bampi, M.J., Fusco, J.M. Relatrio do Estudo de Definio do Modelo timo de Regenerador da PETROBRAS CENPES/DIPRIND/SECRAQ Relatrio Interno Sept. 1996. Ramos, J.G. Evoluo da Tecnologia de FCC na PETROBRAS, 2o Encontro Sul-Americano de Craqueamento Cataltico Recife, Brazil, Aug 1996. Morgado Jr., E., Leite, L. F., Torem, M.A., Pravia, O.C. Design of FCC catalyst for residue processing at Petrobras, 2nd European Catalyst Technology Conference, Belgium. Feb. 26-27, 2001. Morgado Jr., E., Leite, L. F., Torem, M.A., Pravia, O.C. New and Improved: Residue FCC Catalyst, v7 n1 Jan. 2002, Hydrocarbon Engineering. Morgado Jr., E., FCC catalyst with enhanced porosity Part III Studies on REGAP/REFAP formulations, Petrobras Technical Report - DICAT 17/98, March 1998. Morgado Jr., E., FCC catalyst with enhanced porosity - Preparations at pilot plant scale, Petrobras Technical Report - DICAT 17/98, October 1997. (11)_Leite, L.F., Schlosser, C.R., Ramos, J.G.F., Yung, K.Y. Synergy effect of accessibility catalyst, Petroleum Technology Quarterly, Spring 2000, 37-43. improved