Ultra-Selective FCC Process with Downflow Reactor and Optimized Catalyst System

A. Pinho, K. Maeshiro, W.K. Huziwara, E. Morgado, Jr., M.B.B. Almeida, M. Silva and N. Patricio, Jr. PEPETROBRAS R&D Center, Rio de Janeiro, Brazil Abstract
Many recent developments in the FCC area have focused on reducing the contact time between catalyst and hydrocarbon vapor to improve product selectivity: lower delta coke on catalyst, and higher selectivity to gasoline and light olefins. Nevertheless, very special conditions should be used to benefit from such short reaction times, as clearly indicated in pilot tests carried out at PETROBRAS. The downflow reactor provides significant selectivity advantages, mainly in terms of coke and olefins, due to its much more uniform gas-solids flow pattern. However, in downflow reactors, the catalyst residence time and catalyst holdup is lower, considering the same hydrocarbon residence time used in a riser. Thus, for obtaining the adequate conversion levels, higher catalyst to oil ratio, higher reaction temperature or more active catalyst would be necessary. Fortunately, the continuing development of new catalyst technologies has made possible to work with downflow systems without any harm on conversion levels, using regular FCC operating conditions. Experimental studies carried out at a pilot downflow unit, using a pilot riser unit as reference, showed advantages in conversion, LPG and propylene. Following these studies, PETROBRAS will revamp one of its FCC units into a downflow catalytic cracker.

1. Introduction
Historically, the fluid catalytic cracking process (FCC) has been geared towards the production of maximum gasoline. This traditional scenario has changed dramatically in the last years. There is a growing demand of diesel fuel in EU and some other countries. Even more important is the strong tendency to increase production of light olefins, which are used as building blocks for petrochemicals, for instance. They can be also used for alkylates production, suitable to be added as octane booster in the gasoline pool. PETROBRAS has to face an additional challenge: to match the increasing demand of light olefins to the increasing supply of Brazilian heavy crudes from Campos basin, like Cabinas and Marlim, which are heavier than the normal imported ones, resulting in a higher vacuum residue yield: approximately 30 33 wt%. Moreover, these crudes contain higher amounts of nitrogen compounds, asphalthenes and metals. Consequently, the percentage of 570C+ fraction in the feedstocks processed in the FCC surpass 20 vol%. Typical API density is below 20, while Concarbon Residue is above 2 wt%.

Many recent developments in the FCC area have focused on rapid separation devices to reduce post-riser cracking, reducing thermal cracking and dilute phase catalytic cracking. Dilute phase cracking increases dry gas production and causes additional coke formation on the surface of the catalyst. High hydrogen transfer selectivity is also characteristic of this secondary reaction process, resulting in octane loss and reduced LPG olefinicity through formation of C3/C4 saturates, especially isobutane. Many licensors and refiners developed their rapid separation devices, including PETROBRAS, which uses its own proprietary device: the PASS technology (1). Although these devices do increase LPG olefinicity due to reduction of hydrogen transfer and thermal cracking in the separation vessel, their use offers a limited approach in terms of increasing light olefins production. PETROBRAS proposal to achieve deeper conversion from heavy feedstocks, suitable to produce light olefins as well as to obtain significant abatement in fuel oil, is to carry out catalytic cracking by using a downflow reactor.

2. Theoretical Discussions
In the conventional FCC process, the catalyst particle moves in an upflow reactor, or riser, against gravity. The backmixing of solids inside riser reactors results in a wide variation in residence times for the solids, as well as clustering and radial solids segregation. However, due to a strong tendency for coke formation, the FCC process demands a very short, but uniform, contact time between gas and solids. A distinguishing feature of all riser reactors is the slip factor, the ratio between catalyst and hydrocarbon velocities. In a riser reactor both catalyst and hydrocarbons move vertically upward, but the hydrocarbon moves faster. Most of the hydrocarbon moves in the middle of the reactor, while catalyst moves near the wall (2). Typically the hydrocarbon vapor velocity is 2 to 3 times that of the catalyst. Thus, while the catalyst takes 4 to 8 seconds to pass up the full length of the riser, the hydrocarbon may take only 2 to 3 seconds. In contrast to what happens in a riser, particles in a downflow reactor move with gravity. Particle flow in downflow reactors is much more uniform radially than in upflow reactors. Backmixing of solids is reduced, leading to shorter and more uniform solids residence times. Hydrocarbon and catalyst have an almost equal residence time of around 2 seconds in a downflow reactor. In a riser, a great part of conversion occurs in the reactor entrance region, where catalyst comes in contact with the fresh feed. After the first few meters, the riser selectivity to noble products, like gasoline, deteriorates, since most of the catalyst is already deactivated by coke. In a downflow reactor, there is relatively low conversion in the entrance region since the solids are not held up in the entrance region as much as they are in a riser (3). Thus, conversion occurs throughout the whole downflow reactor and gas will come in contact with fresh catalyst at any axial location. On the other hand, conversion in risers benefits from backmixing and higher catalyst holdup in the entrance region, and a large amount conversion will be obtained by thermal cracking, when fresh hydrocarbon comes into contact with a large amount of coked catalyst. The downflow provides significant selectivity advantages, in particular in terms of coke and olefins due to its much more uniform gas-solids flow pattern (4). However, in downflow reactors, catalyst residence time is lower at equal hydrocarbon residence time compared to a riser, and catalyst holdup is lower. Therefore, to obtain adequate conversion levels, a higher catalyst to oil ratio, a higher reaction temperature, or more active catalyst will be desirable in a downflow reactor to compensate for lower catalyst holdup and a lower catalyst residence time. Fortunately, new developments in catalyst technology make possible to run downflow systems without any penalty on conversion levels, at conventional operating conditions.

3. PETROBRAS Studies 3.1. Pilot Units

CENPES - Petrobras R&D Center - has been working with downflow FCC reactors since 1995. In 1996, PETROBRAS started up its first pilot FCC downflow reactor, a non-circulating unit, without regeneration. To establish the differences in selectivity between downflow and riser reactors, a specific study was carried out, using CENPES pilot riser as reference. A commercial FCC gas oil feedstock from Campos Basin (Cabinas) and an equilibrium catalyst without ZSM-5 were used in the study. Feedstock and catalyst properties are shown in Table 1 and 2, respectively. In the comparison at constant coke on Table 3, for these specific operating conditions and catalyst, a clear advantage in conversion, LPG and propylene could be observed at temperatures as low as 550C. A second pilot unit, equipped with the regenerator side, started up in 2000 and confirmed the promising previous results. Table 1 Feedstock Properties API 18.6 Sulfur (wt%) 0.63 Basic Nitrogen (ppm) 1001 Total Nitrogen (ppm) 3069 CCR (wt%) 0.6 Aniline Point (C) 93.2 Table 2 Catalyst Properties Chemical Analysis Al2O3, wt % SiO2, wt % RE2O3, wt % P2O5, wt % Physical Properties Surface Area, m2/g Micropore Area, m2/g Mesopore Area, m2/g Unit Cell Size, nm Table 3 Riser vs. Downflow Comparison Type of Reactor Reaction Temperature Conversion Catalyst-to-Oil Delta coke Yields: Coke Fuel Gas Ethylene Hydrogen LPG Propylene Butene Gasoline LCO Bottoms C wt % Riser 550 72.5 7.8 1.13 8.8 4.8 0.94 0.60 17.9 4.8 8.6 41.0 15.9 11.6 Downflow 550 74.8 8.7 1.02 8.8 4.8 1.68 0.17 20.4 6.6 9.7 40.8 12.2 13.0 36 58.8 2.14 0.54 137 109.6 27.6 2.426

wt % wt % wt % wt % wt % wt % wt % wt % wt %

3.2.

Cold Models

The entrance region constitutes a substantial part of the downflow reactor because of the shorter catalyst contact time. Therefore, a good radial catalyst distribution becomes more important to promote catalyst and feedstock intermingling. The quick separation of gas and solids after the downflow reactor is another critical point to be studied, since one aims at avoiding hydrogen transfer and thermal reactions. Design and optimization of distribution and separation devices must come hand in hand with experimental tests. Thus, a large and cold FCC model, which started up in 2001, was built at SIX Paran State - to support these technological developments. The cold model is 30 meters height and it features a 9 meters height downflow section with 440 mm inner diameter and a 26 meters height upflow section with 440 mm inner diameter. It uses a 440 kW air compressor, with an air capacity of 20 t/h, circulating up to 120 t/h of FCC catalyst. Some parts of the cold model unit in both upflow and downflow sections are made in Plexiglas to allow visual inspection. All the process variables of pilot plant unit are controlled and monitored by an up-to-date Distributed Control System (DCS). The use of this large cold model enables Petrobras to carry out experimental tests in research, development and optimization of a downflow reactor in the same operating conditions founded in industrial setup. In the experimental tests to evaluate the performance of the downflow reactor devices, such as the distributors and separators, state-of-art techniques have been used to evaluate solid-gas flows. Additionally, Petrobras established a cooperation agreement with Universities in Brazil and abroad, such as University of Tsinghua (China) and UNICAMP (Campinas State University) to consolidate the results obtained in these experiments.

4. A Special Catalyst for a Downflow Unit

In order to maximize the advantage of the catalyst and hydrocarbon distribution profile in the reaction medium provided for by downflow reactors, specially designed catalysts should be employed. The hydrocarbon mass transfer rate within the catalyst particle, as well as the mass transfer rate of the products to the outside of the particle become more important as far as the effective catalyst residence time in the reaction medium is shorter. Thus, the catalyst architecture should be such as to provide a high accessibility to the active sites and quick desorption of the products, preventing the non-selective cracking as well as the over-cracking of gasoline. High activity catalysts not only by the use of a relevant amount of active constituents having micro (zeolites) and mesoporous (matrix) structure, but mainly by promoting enhanced accessibility (5) have been developed for this particular purpose. The novel modified catalyst was compared to the reference catalyst manufactured via conventional technology, at constant ingredient intake. Their properties are summarized in table 4. Table 4 Properties of conventional and high accessibility catalysts Al2O3, wt % SiO2, wt % RE2O3, wt % ABD, g/ml Surface Area, m2/g Micropore volume, m2/g Mesopore Area, m2/g Conventional 32,0 63,4 2,03 0.71 287 0.103 66 High Accessibility 32,9 63,2 1,98 0.70 362 0.115 110

AAI, arbitrary units

1.9

5.9

AAI is the accessibility index measured according to the proprietary method developed by Akzo Nobel (6). Notice that the AAI of the novel catalyst was three times higher than that of the reference. Also, a remarkable increase in porosity in the mesopore range (2-50nm) was observed. The catalysts were steam deactivated (788C / 5h) and evaluated using the new circulating pilot plant unit provided with a downflow reactor, which processed the same gasoil characterized in table 1. The unit inventory was 2 kg and the flow rate of gasoil was 1.7 kg/h. Normally employed conditions in industrial riser reactors were applied: reaction pressure 0.1 kgf/cm2G, contact time 2 seconds, reactor exit temperature at 540C, and in the stripper 500C. The catalyst to oil ratio was varied in the range of from 6 to 9 by altering the feed temperature in the adiabatic reactor. At constant conversion the modified catalyst pointed towards an improvement in the coke, fuel gas and gasoline selectivity. The results at constant coke are summarized in table 5. Enhanced conversion levels could be reached by using the high accessibility catalyst at catalyst/oil ratio, typical of upward flow reactors. Fuel gas and hydrogen yields were reduced and the light olefins yield was increased. On the other hand, the best result was the remarkable improvement in bottoms conversion relative to the base case. This means that the disadvantage presented in the item bottom conversion in downflow relative to a riser, as described in table 3, may be compensated by using the high accessibility catalyst system. The results proved that the combination of a dowflown reactor and high accessibility catalyst leads to maximum conversion into valuable products in a synergistic way.

Table 5 Downflow Reactor Results: Conventional vs. High Accessibility Catalyst Catalyst Reaction Temperature Conversion Catalyst-to-Oil Delta coke Yields: Coke Fuel Gas Ethylene Hydrogen LPG Propylene Butene Gasoline LCO Bottoms C wt % Conventional 540 75.1 7.6 1.11 8.5 3.9 1.2 0.10 18.3 4.8 9.4 44.4 12.6 12.3 High Accessibility 540 85.5 10.3 0.83 8.5 3.5 1.1 0.05 19.5 6.1 9.3 54.0 9.6 4.8

wt % wt % wt % wt % wt % wt % wt % wt % wt %

85 83 81

Conversion, wt%

79 77 75 73 71 69 67 65 5 6 7 8 9 10

Catalyst-to-oil, wt/wt

Figure 1. Conversion vs. Catalyst-to-Oil ratio ( ) Conventional (

) High Accessibility

9.9 9.4 8.9

Coke, wt%

8.4 7.9 7.4 6.9 6.4 69 71 73 75 77 79 81 83 85

conversion, wt%

Figure 2. Coke vs. Conversion ( ) Conventional (

) High Accessibility

5.5 5.3

Propylene, wt%

5.1 4.9 4.7 4.5 4.3 4.1 3.9 7 7.5 8 8.5 9

Coke, wt%
Figure 3. Propylene vs. Coke ( ) Conventional (

) High Accessibility

5. Revamping a Commercial FCC Unit

Petrobras has gained a lot of experience in FCC design and technology since the 80s when it revamped its FCC units with in-house technologies to increase the use of heavier feedstocks. More recently three residue grassroots units were completely designed by PETROBRAS staff, increasing the total PETROBRAS FCC installed capacity to 82 000 m3/day. The experience that was accumulated along these years will be used to revamp one of its FCC units into a downflow catalytic cracker unit with total investment around US$ 10 million. In a first moment, PETROBRAS will install the downflow reactor and verify its performance, using regular FCC operating conditions. Reactor temperature will not be higher than 550C and catalyst to oil ratio will be around 7 - 8. Nevertheless, other innovations shall be implemented in a second stage to take full advantage from downflow reactors unique features, which permit the FCC to work in a more severe operating window. Some FCC processes launched in the market have proposed an increase in reaction severity by the increase in reaction temperature and catalyst to oil ratio. Nevertheless, two main constraints must be removed in order to increase catalyst to oil ratio: energy balance and fluid dynamics. High catalyst to oil ratios are limited in riser reactors, since there is a maximum amount of catalyst that can be pushed upward by the gas against gravity, the so-called choking limit. For regular operating FCC conditions and feedstocks, the maximum catalyst to oil ratio for the riser is found to be approximately 10 (3). In the case of a downflow, there is not choking limit since both gas and particles move in the direction of gravity. Besides, the absence of choking limit, the lower delta coke obtained would favor energy balance and, consequently, an increase in the catalyst to oil ratio.

The use of ISOCAT will permit an additional increment in catalyst to oil ratio. This patented technology (7) makes use of catalyst cooling in an unusual manner to independently control catalyst circulation and the heat balance. This is done by splitting the regenerated cooled catalyst stream so that a part is returned to the regenerator and another is mixed with the hotter regenerated catalyst going to the reaction zone. ISOCAT combined with a downflow reactor will allow to push the catalyst to oil ratio up to the energy balance limit, deepening conversion and maximizing light olefins production. Another increment in severity conditions can be obtained by increasing substantially the reactor temperature. Again, downflow reactors present advantages, since at the low rate of thermal cracking reactions that occur in a downflow system a high reaction temperature does not produce substantial increase in dry gas yield and gasoline degradation. Another point worth mentioning is the ZSM-5 role at different temperatures. Under typical FCC operating conditions, ZSM-5 increases substantially improve propylene and butene yields, but also C5 olefins. The overall gasoline olefin contents are dominated by the behavior of C5 olefins, since C5 olefins account for about one-third to one-half of the gasoline olefins. Therefore, at regular FCC reaction temperatures, gasoline olefins remain approximately constant. Nevertheless, at temperatures above 565C the C5 olefins can be reacted into lighter olefins, improving gasoline quality and increasing light olefins production. More studies must be carried out to explore ZSM-5 usage and temperature influence on propylene in downflow reactors, since feeds or catalysts or other change can affect results differently for different systems (8).

6. Conclusions
The high competitiveness observed in the oil industry demands technological innovations for a better positioning of the refiner. FCC technology has to face tough challenges such as processing heavy crudes and upgrading the bottom of barrel and, at same time, producing light olefins to attend its growing market. Downflow reactors appear not as an evolutionary trend for the FCC technology, but as a revolutionary one. Advantages do not come only from improvements in selectivity obtained by its much more plug flow-like pattern, but also from the possibility to operate in a more severe operating window, with higher catalyst to oil ratio and reactor temperature. Some recent changes in catalyst technology made possible to maximize the benefits obtained from downflow systems, which assures deeper conversion and maximum light olefins production.

References
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7. Ramos, J.G.F., Fusco, J.M., Bampi, M.J., Sandes, E.F., Barros, F.C.C., Medeiros, J., Santos, C.F.M., Dubois, A.M., Zech, I.A., Einsfeldt, M., Rocha, C.S., Process for Fluid Catalytic Cracking of Heavy Feedstocks, US 6,059,958, 2000. 8. Zhao, X., Roberie, T.G., ZSM-5 Additive in Fluid Catalytic Cracking. 1. Effect of Additive Level and Temperature on Light Olefins and Gasoline Olefins, Ind. Eng. Chem. Res., 38, 3847-3853, 1999.