Catalyst Accessibility: a new factor on the performance of FCC units.

E. Morgado Jr., M.B.B. Almeida and R.D.M. Pimenta

PEPETROBRAS R&D Center, Rio de Janeiro, Brazil

Abstract
Accessibility has been recently claimed as an important characteristic of the FCC catalysts. This property is specially raised when diffusion limitation becomes a critical issue. This is the case when one takes into account the new trends in FCC operation such as the processing of heavier and lower cost feedstock and the reduction in contact time between catalyst and hydrocarbon vapor. Manufacturing technologies have been developed aiming at enhancing porosity and accessibility and commercially proven advantages have been achieved with these new generation of catalysts. However, the accessibility behavior of the catalysts after entering the commercial unit is not fully understood since different phenomena occur in the FCC process that results in substantial alteration of the original accessibility of the fresh catalyst. Primarily, steam and contaminant metals play an important role on defining the accessibility of the final equilibrium catalyst. In the regeneration conditions, steam cause pore structure opening and some contaminant metals can promote surface blockage, thus generating opposed effects on the catalyst accessibility. In the present work, catalysts from different FCC units at Petrobras, including two RFCC units, were characterized focusing on the accessibility aspect. The results were related to the type of catalyst, to the influence of hydrothermal conditions and presence of contaminants in the unit. The consequences on the commercial performance have also been discussed.

Introduction
The fluid catalytic cracking process (FCC) plays a crucial role in the refining strategy of PETROBRAS. In Brazil, the company has 13 FCC units (FCCUs) currently processing over 80,000 m3/day of oil with average CCR of 2.5, typically untreated gas-oil with some incorporation of atmospheric residue (ATR). Two of these are residue FCC units (RFCCs) specially designed by Petrobras1, which are successfully converting 13,000 m3 per day of 100% ATR with CCR above 6.0. Continuous hardware and catalyst innovations in residue upgrading have allowed PETROBRAS to increase in ca 70% the FCC processing capacity in the last six years, even though the feedstock decreased in quality. Such achievement was in part ascribed to the emphasis given on the catalyst technology development as a key parameter to enhance the FCC unit performance. Diffusion limitation has become increasingly important for the FCC process because of the recent 2,3 advances in residue processing and short contact time operations . It is recognized that mass transfer tends to become the rate-controlling step in modern FCC units. As architecture of the catalyst may now play a role even more determining than matrix and zeolite acidity, catalyst manufacturers have been focusing their attention on improving the accessibility to the active sites3-13. The term Accessibility is currently used to describe the mass transfer ability of reactants through the catalyst porous structure and of products diffusing out of the catalyst particle. A simple and fast method for quantification of this property has been developed by Akzo Nobel, which measures the rate of penetration of large hydrocarbons into FCC catalyst particles. No reaction is involved but simply a 5-9,12,13 . The relative measurement of resistance to mass transfer under non-steady state diffusion accessibility index (AAI) as calculated from this test has proven its potential for catalyst development and in describing diffusion related problems in FCC units7-13. It is known that accessibility is largely determined by catalyst manufacturing and different assembly technologies have been developed in order to provide more accessible catalysts with acceptable physical properties to the market4,7,9-11. Petrobras and Akzo Nobel have been employing two

technologies, which produce, at constant ingredient intake, commercial catalysts with improved accessibility. On the other hand, catalyst can be further affected by aging mechanisms occurring in the FCC unit, such as hydrothermal deactivation and metals deposition. These two phenomena are known to cause detrimental effects on the concentration and type of active sites, but also can drastically modify the pore structure with significant influence on the accessibility. The behavior of the catalyst accessibility in commercial FCCUs is not widely known, especially due to the many variables related to the type of catalyst and operation conditions. By examining equilibrium catalysts (E-cat), Akzo-Nobel 7-9 observed that they were less accessible than the corresponding fresh catalyst and that AAI decreased with contaminant metals and catalyst aging in most cases. It is evident that catalyst architecture changes under FCC unit conditions and only the E-cat accessibility will represent the real ability to avoid or attenuate diffusion restrictions. Nevertheless, limited number of studies concerning architecture of the catalyst in equilibrium state has been reported. The investigation on the behavior of the catalyst accessibility in all Brazilian FCCUs is the focus of the present work. Other E-cat characteristics such as chemical, textural and morphological properties have been examined, considering the accessibility aspect. The possible mechanisms to explain the accessibility behavior of the catalyst after entering the FCC unit were discussed and a mental model was proposed.

General behavior of catalyst accessibility in Brazilian FCCUs

The accessibility data of equilibrium catalysts from four FCCUs are plotted in figure 1, illustrating the normal range of AAI levels observed in the Brazilian units. A summary of all cases ordered according to the catalyst technology is shown in table 1, including the AAI comparison between fresh and equilibrium catalysts as well as the average metals content on the E-cat. Technologies B and C boost accessibility relative to the conventional catalysts based on technology A. As reported elsewhere3, the concept of triple particle catalyst (TPC) applied for the RFCC cases in Petrobras regards the use of highly accessible catalysts combined with appropriate flushing catalysts.
12 11 10 9 FCC-11 FCC-9 FCC-5 FCC-4

AAI

8 7 6 5 4 3 25/08/00 08/09/00

22/09/00

06/10/00

20/10/00

03/11/00

17/11/00

01/12/00

15/12/00

29/12/00

12/01/01

26/01/01

09/02/01

23/02/01

09/03/01

23/03/01

06/04/01

Date

Figure 1 Accessibility measured in the equilibrium catalysts of some Petrobras FCC units Excluding the RFCC cases, all equilibrium catalysts showed higher accessibility than the fresh counterpart. The AAI increase from fresh to equilibrium was of, at least, 50%. On the other hand, when one plots the relative increase of AAI against the fresh AAI (figure 2), the curve clearly demonstrates that the least accessible catalysts were the most susceptible to the AAI increase. Because of this distinct AAI response, catalysts type A ended up in the equilibrium state with accessibility values very close to those from catalysts type B. Type-C catalysts were able to retain an improved E-cat accessibility and overall there was a reasonable correlation between accessibility in the fresh and equilibrium states.

20/04/01

Table 1 - Characteristics of the E-cats and relative AAI behavior FCCU Catalyst Technology Fresh FCC-1 FCC-2 FCC-3 FCC-4 FCC-5 FCC-6 FCC-7 FCC-8 FCC-9 FCC-10 FCC-11 RFCC1 RFCC2 A A A A A A B B C C C TPC TPC 0.7 0.8 1.1 1.3 2.3 2.5 4.1 3.2 5.5 5.0 6.7 6.7 10.5 AAI E-cat 5.8 5.4 6.7 5.3 7.0 5.7 6.2 7.3 8.9 9.7 10.3 6.6 8.4 Ni 980 2800 2300 2400 430 900 3000 980 2000 3600 2500 7100 4500 V 530 2600 1700 2300 180 2300 2400 530 1400 1800 1800 3000 4700 Metals Contents (ppm) Ca -300 200 200 <100 900 100 -100 300 200 -400 Na 2400 3200 3000 3500 2700 4700 3300 2400 3100 3400 4400 5300 4000 Fe 3600 2800 2900 3800 4300 3700 3600 3600 3200 3200 3300 3700 3700 Added Fe 300 600 300 700 200 1000 400 300 600 1100 500 700 800

8 00 y = 4 62 ,72 x- 1,1886 7 00 6 00 5 00 4 00 3 00 2 00 1 00 0 0 1 2 3 4 5 6 R 2 = 0 ,94 4 3

% re la tive AAI incre a se

F re sh AAI

Figure 2 Influence of the starting fresh AAI on the relative increase in accessibility

Understanding the AAI increase behavior

Hydrothermal effects and metal contamination are the most suspicious phenomena to affect accessibility in the FCC unit. As metals deposition is believed to cause a negative impact on accessibility, this phenomenon is certainly not prevailing. Indeed, AAI has increased in spite of the metals content ranging from 7000 to 13000 ppm in the different FCCUs (1 to 11) and there was no correlation between the relative AAI increase and the average content of total metals or of any specific contaminant metal. Therefore, the investigation was primarily focused on the hydrothermal process.

Steaming Experiments
Conventional steam deactivation protocols yield increased AAI relative to the corresponding fresh catalyst 9,12-13. It indicates that the steaming process is likely causing the AAI increase in the commercial unit. This encouraged us to carry out steaming experiments with some of the fresh catalysts supplied to the Brazilian FCCUs. As the standard deactivation applies unrealistic high temperature and steam partial pressure (800C/100%/5h), some runs were conducted under less

severe conditions, in order to approach typical regenerator conditions. The results are summarized in table 2 with the corresponding fresh (calcined 600C) and E-cat properties as references. Table 2 Accessibility and BET surface area (in brackets) of the steamed catalysts Steaming T (C) 600 (fresh) 650 800 650 800 E-cat % 0 30 30 100 100 FCC-4 1.3 (284) nd (249) 3.0 (225) 3.4 (208) 5.2 (185) 5.3 (124) FCC-5 1.5 (295) nd (255) 2.6 (233) 4.6 (218) 4.4 (191) 6.9 (171) FCC-9 5.5 (377) 7.1 (327) 10.5 (284) 11.1 (262) 14.1 (241) 8.9 (182) FCC-11 6.7 (426) 9.3 (367) 11.1 (316) 15.7 (296) 17.3 (249) 10.3 (210)

Differences between steamed and E-cat surface areas were mostly due to the absence of metals. Metals were not applied since previous experience showed no AAI difference between nonimpregnated and metal-impregnated samples via the classic Mitchell method14. Steam pressure showed a stronger effect on deactivation than temperature. Steaming caused the expected AAI increase behavior in all cases. The accessibility of the catalysts type C approached the equilibrium AAI at more realistic steaming conditions, whereas those of type A needed maximum severity. This is in contrast with the behavior depicted in Figure 2. Apparently, the fresh catalysts with lower accessibility were more susceptible to the AAI increase in the real condition. One possible explanation may derive from the evidence of a skin on the surface of most types of FCC catalysts8,12, which appears to be denser than the interior. The catalysts type A are expected to have skin of lower permeability than that in the high accessibility catalysts type B/C. However, assuming this denser skin becomes less refractory at elevated temperatures15 and combining this with the abrasive environment in the real FCC unit, one could imagine a more extensive formation of microcracks on the outer surface of the catalysts type A, which might explain its larger increase in AAI. Another large E-cat sample from FCC-5 unit was also submitted to steam deactivation in pilot plant (fluidized bed) in order to verify the impact on accessibility. As shown in table 3, the equilibrium catalyst suffered no modification on accessibility, although surface area decreased further. Table 3 Effect of steaming (690C/100%H2Ov) on accessibility and surface area of the E-cat Steaming Time (h) 0 4 24 48 AAI 6.4 6.5 6.7 6.5 BET SA (m2/g) 159 149 143 143

Pore Volume Distribution

Selected steamed and equilibrium catalysts, as well as their corresponding fresh samples, have been analyzed with respect to the pore volume distribution (PoVD), as measured by mercury intrusion porosimetry. The meso and macropore range, from 30 to 10000 angstrons pore diameter, are covered with this technique. The results indicated an interesting pore structure evolution while steaming

severity increases. Mesopores (30-500 ) starts to be developed, probably from the shift of small pores (< 30 angstrons) into larger ones, and then macropore contribution tends to increase, approaching the E-cat pore structure. This is illustrated in figure 3 for two cases with conventional and high accessibility catalysts. Overall, average pore diameter and macropore volume tends to increase with steaming in the same direction as accessibility. However, pore volume distribution profile could not be well combined with accessibility data. Steamed and equilibrium catalysts with the same AAI values showed distinct PoVD profiles (FCC-4) and in general, E-cats presented narrower peaks in the macropore region. On the other hand, all steamed E-cat samples characterized in table 3 showed exactly the same PoVD as the original E-cat, confirming the unchanged architecture.
0,35 0,30 0,25
Fresh 650C/30%steam 800C/100%steam AAI=5.2 E-CAT AAI=5.3 AAI=1.3

FCC-4

0,35 0,30 0,25

Fresh 650C/30%steam

AAI=5.5 AAI=7.1

FCC-9

800C/100%steam AAI=14.1 E-CAT AAI=8.9

dV/dLog(D)

0,20 0,15 0,10 0,05 0,00 10 100 1000 10000

dV/dLog(D)

0,20

0,15 0,10 0,05 0,00 10 100 1000 10000

Pore diameter, angstrons

Pore diameter, angstrons

Figure 3 Mercury Porosimetry of fresh, steamed and equilibrium catalysts from FCC-4 and FCC-9 It is worth mentioning that the apparent bulk density (ABD) of the catalyst usually increases from the fresh to the equilibrium state. In principle, the formation of large pores as demonstrated above would favor the decrease in ABD, but there are other contrary driving forces such as the collapse of small pores and the attrition in the FCC unit, which causes an improved particle shape and better packing behavior, tending to increase measured ABD.

Density separation
AAI could be analyzed as a function of the age fraction in the equilibrium catalyst. This is achieved by the use of a procedure that has been developed for the separation of E-cats by density16. The E-cat from FCC-7 has been submitted to the density separation method. Data are summarized in table 5. The separation could be verified for the differences in surface area. Accessibilities of all fractions were comparable to the equilibrium AAI and higher than the fresh one. AAI did not change from the lightest (fraction-1) to the heaviest fraction (fraction-4), indicating no aging effect on the accessibility. It is worth noticing that the AAI is already increased in the lightest fraction, thus indicating that the AAI should rapidly increase in the early stages of contacting the fresh catalyst to the unit. Table 5 Results of density separation on the catalyst from FCC-7 BET S.A. (m2/g) Fresh Fraction 1 Fraction 2 Fraction 3 Fraction 4 E-cat 302 191 140 100 81 135 AAI (a.u.) 4.1 6.4 6.4 6.0 6.4 6.2

Scanning Electron Microscopy

Could cracks or pore openings on the outer surface of the equilibrium FCC catalysts be responsible for the AAI increase? To answer this question, some Brazilian E-cats were submitted to Scanning Electron Microscopy (SEM) analysis at different magnifications (300x, 1500x and 20000x). For morphology comparison, the corresponding fresh samples were analyzed as well. Catalysts from FCCs 2, 3, 5, 10 and 11 were selected for SEM analysis. From the images of lower magnification, it was in general observed the fresh catalysts with more irregular particles showing much rougher surfaces than the equilibrium ones, as a result of the particle surface abrasion in the unit. Assuming the inhomogeneous character of FCC catalysts15, it is difficult to evaluate until what extent this fact might influence the architecture of an E-cat in comparison with the corresponding artificially steamed catalyst, which retains the surface roughness of the fresh counterpart. As a significant variation in morphology was found among the particles within the same sample, SEM was very much inconclusive to explain the accessibility differences. Overall, there was no clear evidence of cracks or pore openings that could easily justify the increased AAI behavior.

Relationship with FCC unit conditions

A survey has been made among all Brazilian units here studied to compile as much information as possible, such as feed characterization, operational conditions and hardware features, which could be related to the relative AAI behavior. The relative percentage change in AAI were used as the dependent variable in a multiple linear regression analysis with the following independent variables taken into account: Catalyst : Fresh and E-cat AAI; vanadium, nickel and added iron in E-cat; Catalyst Addition Rate; Feed : density; wt% sulfur; Carbon residue; basic nitrogen; vol% fraction of ATR; vol% fraction of coker gasoil; vol% fraction of coker naphtha; FCCU conditions and features : Total feed rate; Reaction Temperature; Riser Pressure; Regenerator Pressure; Regenerator Temperature (dense and diluted phase); Feed Temperature; Steam rates (normalized per feed rate) for stripping, for dispersion and for lifting; Water addition in the Riser; Regenerator mode (partial or full); Residence time in stripper; Residence time in Regenerator. Some conditions could not be estimated for all cases (eg. CO/CO2 and %H/coke ratios), hence not being included as statistical data input. Steam partial pressure was assumed approximately constant for all units (20-30%). The point of catalyst addition into the dense phase was a common feature. As the number of variables (27) exceeded significantly the number of cases (11 FCCUs), the forward stepwise regression has been applied to estimate the significance of the effects. The statistical analysis revealed the fresh AAI as the only significant variable to have an effect on the AAI %change. There was no correlation with the other FCCU parameters. Although the residual analysis did not show a good reliability for the statistics, the result is corroborated by the strong correspondence observed in figure 2. The final result were the same when the two RFCCs (null and negative AAI behavior) were included in the statistics.

Understanding the AAI behavior in the Brazilian Resid FCC units

The cases of accessibility loss reported by Akzo-Nobel are usually related to the total amount of metals deposited on the catalyst 7,9,10. However, some metals seem to have no significant impact on accessibility. Vanadium and sodium easily migrate causing destruction of the zeolite pore structure and unlikely reach high enough concentration to form species to block larger pores associated to accessibility. In Petrobras FCCUs and RFCCs, where nickel, sodium and vanadium varied significantly in certain periods, no remarkable alteration in AAI could be noticed whereas surface area 9,17 , was definitely changed. Metals such as nickel, iron and calcium tends to enrich the E-cat surface however the catalyst matrix normally stabilizes nickel in its lattice, preventing it from agglomerating on the outer surface. In contrast, iron easily agglomerates and promptly suppress catalyst accessibility 8,9,17 . More recently, Akzos researchers found due to significant blockage of the outer surface pores out that the only way of mimicking the AAI drop observed in some refineries should consider iron in the deactivation protocol 18.

Several FCCUs suffer significant loss of accessibility primarily due to iron contamination 7-10,12-13. Indeed, this contaminant should be treated separately regarding accessibility problems in the inventory. The added iron in table 1 refers to the contaminant iron, calculated as the total Fe in the Ecat minus the Fe contained in the fresh catalyst (from clay). In the set of cases here considered, added iron was relatively low (below 0.1%) and likely non-deleterious. Previous experience showed FCCUs developing symptoms of iron poisoning at approximately 0.2-0.4wt% added iron on catalyst10,19. Calcium, which is known to have similar surface deposition profile as iron 17,19, was also quite low in Brazilian E-cats. The relatively low contents of these metals, at least in part, could explain the general favorable AAI behavior for the Brazilian units. As verified in table 1, the two RFCCs were the only cases where AAI did not increase. Although a larger amount of metals was deposited on the E-cat, added iron and calcium were within the same low levels as in the other Brazilian E-cats and this would hardly prevail over the steaming effect. Therefore other phenomena have to be considered. The catalyst system used in RFCC-1 and RFCC-2 contains a significant amount of flushing catalyst, respectively 30 and 60wt%. This fraction is an E-cat, already pre-deactivated, thus no further AAI increase is expected as demonstrated in table 3. Moreover, the fresh fraction contains highly accessible catalysts, which are less prone to the AAI increase (fig. 2). In summary, the catalyst system in the RFCCs is intrinsically less susceptible to the steaming effect if compared to the other cases. This fact, in combination with the high metals load, should be responsible for the net effect of equal or slight decrease in accessibility.

Iron contamination in the Brazilian Resid FCC units

Since the start-up of the Brazilian RFCCs, their equilibrium catalysts have been showing normal levels of contaminant iron. However, three short events of iron contamination were verified. In RFCC-2 the first iron excursion occurred on February 2000 and the second one on August 2001, both caused by contamination with slop-oil, which has to be processed in the distillation unit from time to time. As shown in figure 4, a remarkable loss in catalyst accessibility confirmed the striking effect of iron poisoning (added Fe = 0.25-0.55%) in these two periods. Besides AAI, other dependent E-cat properties such as ABD, BET surface area and MAT activity were statistically analysed as a function of all contaminants content. Accessibility was highly correlated with iron content, whereas surface area and MAT activity were primarily a function of the vanadium content. Although not so evident in the second excursion, ABD was clearly reduced with added iron in the first excursion.
0,95 10

First excursion
0,90 0,85 0,80

Second excursion

Fe
0,75 0,70

AAI
7

% Fe

0,60 6 0,55 0,50 0,45 0,40 0,35 0,30 28/08/99 3 13/02/02 4

06/12/99

15/03/00

23/06/00

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Figure 4 AAI behavior during two excursions of iron contamination in RFCC-2 7

AAI

0,65

Three samples corresponding to decreasing AAI values caused by iron poisoning were collected during the second excursion and examined by SEM. Except for iron, the other metals showed comparable contents in these samples. In the sequence illustrated in figure 5, one can see the increasing density of nodules being formed as iron content increases and AAI drops. The same pattern of nodules formation on the outer surface and its relation with accessibility loss occurred in the first excursion. EDS analysis confirmed iron enrichment of the surface, concentrated on the nodules. Although three types of particles comprise the equilibrium catalysts from Petrobras RFCCs (TPC technology), there was no preferential deposition of iron since nodules appeared in every particle of the contaminated samples. Other commercial experiences outside Brazil confirm this typical iron poisoning behavior and similar effects on AAI 7,12,20, ABD 14,19,20 and morphology 7,8,14,19. The impact on the catalyst pore volume distribution is not often reported. In the present work, some Fe contaminated samples were also analyzed by mercury porosimetry as shown in figure 6. The bimodal profile of the E-cat sample before iron contamination is typical of type C catalysts in major proportion in the RFCC-2 inventory. Iron poisoning seems to have resulted in a shift of the macropore peak to smaller diameter and merging with the mesopore peak. The overall pore volume is not significantly modified. This behavior is in agreement with the mechanism of preferential deposition of iron on the outer surface. The iron deposited as nodules reduces the average diameter of the large pores on the outer surface (decreasing accessibility), but not the total pore volume, since it does not penetrate into the catalyst internal pores.

Figure 5 SEM images of E-cat samples from RFCC-1 during second iron excursion. Left => reference before contamination 07/17/2001 , 0.08%Fe added, AAI = 8.6 ; Center => beginning of Fe contamination 08/10/2001 , 0.16%Fe added, AAI = 5.0 ; Right => maximum Fe contamination 08/17/2001 , 0.26%Fe added, AAI = 3.9 .

0,25 0.39%Fe ; AAI=8.6 0,20 0.57%Fe ; AAI=3.9 0,15

dV/dLog(D) k*mL/g

0,10

0,05

0,00 10

Pore diameter, angstrons

100

1000

10000

Figure 6 Mercury Porosimetry of normal and iron contaminated E-cat from RFCC-2 (2

nd

excursion)

The third case of iron excursion occurred in RFCC-1 on August 2001 and has just been recently realized. The source of Fe is unknown. At that time, not much attention was given to iron contamination and accessibility since a severe catalyst poisoning by sodium was also occurring. In response, a drastic reduction in the E-cat surface area and MAT activity caused inevitable performance problems for a short period. On the other hand, when accessibility data of this period was analyzed a significant AAI drop (from 6.6 to 3.4) was noticed, which could only be related to the increase in contaminant Fe content. Neither nickel and vanadium nor sodium, which varied in a large extent, could be correlated with AAI. This is illustrated in figure 7 and confirms our suspect that drastic reduction in E-cat accessibility is specifically derived from iron poisoning.

9 8 7 6 5 4 3 2

AAI

Fe Na

0,3

0,4

0,5

0,6

0,7

0,8

0,9

1,0

1,1

% metal

Figure 7 AAI dependence on iron and sodium contamination (RFCC-1 unit)

AAI vectors model

AAI in the FCC unit seems to be affected by two opposite driving forces: steaming and metals deposition, which could be represented by opposite vectors. We believe that these forces co-exist in the FCC unit affecting AAI with different magnitudes (vectors intensity), dependent on the type of catalyst, type of feedstock and hardware/operating conditions. The net effect, either AAI increase or AAI decrease can be represented as resultant vectors, as depicted in figure 6. For instance, in most Brazilian FCCUs the steaming effect prevails because of the high susceptibility to steam of the type A catalysts and thanks to the relatively low amount of sintering metals in the E-cat. The result is an AAI increasing vector. In RFCC-1 one force compensated the other. During iron excursions a domination of the descending vector was evident.

Steaming
Macropores Mesopores shift Surface microcraking

Metal deposition
Maybe only iron is the big concern Surface plugging

AAI vectors

The resultant vector will depend on which factor will prevail in the FCCU according to the type of catalyst, type of feedstock (sintering metals) and operating conditions

AAI increase

AAI decrease

Figure 8 Mental model to rationalize AAI behavior in FCC units

Accessibility and performance of the Brazilian FCC units

Introduction of high accessibility catalysts has been very successful in Petrobras units, not only for the RFCCs1,3, naturally operating at diffusion limited regimes, but also for those conventional units whose separation devices were revamped to reduce thermal cracking and shorten reaction time2,11. Measurable benefits were observed in four of the seven units using enhanced accessibility catalysts. Commercial trials in FCC-8 and FCC-10 were especially elucidating since the catalysts with enhanced accessibility progressively replaced their counterparts with exactly the same ingredients composition. Therefore, only architecture has been changed. In both cases the modified catalyst presented superior performance, regarding to conversion and gasoline yields. In the FCC-10 unit, processing gas-oil with almost 30% atmospheric residue, a clear improvement in bottoms conversion was verified as well. The advanced catalyst system designed for the new RFCCs3, containing particles of high accessibility, resulted in excellent performance. Besides that, it proved to be robust enough to bear severe metal contamination as characterized above. This can be illustrated with the comparative results obtained in RFCC-1 before and during iron contamination with severe drop in E-cat accessibility. Short periods could be selected for comparison within the most similar conditions allowed by the dataset. As shown in table 6, there was no evidence of conversion loss due to iron contamination, in agreement with the graphical time trend. Catalyst performance deteriorates very rapidly when the AAI falls below a certain unit-specific value. This value has come to be known as the critical AAI 7,9,13. Such critical point apparently was not reached in Brazilian RFCCs even during iron contamination. The situation would probably be different if the E-cat accessibility was not high enough. Providing highly accessible catalysts to the RFCC inventories, Petrobras is avoiding undesirable losses in conversion and increased slurry yields. Table 6 Conversion comparison in RFCC-2: second Fe excursion vs reference period June 24-25th Reference 70.0-71.9 16.5 7.7 3113 546 713 8.1 11.6 66 5789 4933 4000 3500 125 8.2 August 24-25th Fe contaminated 70.0-71.0 16.8 7.8 3038 546 714 8.3 11.9 66 5101 4327 5400 3700 120 4.4

CONVERSION (wt%) FEEDSTOCK API CCR (wt%) OPERATIONAL COND Feedrate(m3/d) RXT (oC) RGT (oC) CTO CAR (ton/day) E-CAT DATA MAT (wt%) V (ppm) Ni (ppm) Fe (ppm) Na (ppm) BET SA (m2/g) AAI

Conclusion
The increased accessibility and contribution of larger pores, as verified from the fresh to the equilibrium state in most Brazilian FCCUs, showed the same trend as the steam deactivation in laboratory. Somehow and somewhere in the FCC unit, steaming not only deactivates the catalyst but

10

also provokes the AAI increase. This appears to be related with micro-ruptures formed on the catalyst outer surface as a consequence of the hydrothermal shocking in the unit. Unfortunately, this could not be proved by SEM examination. The results suggest that such influence occurs in the early stages after fresh catalyst enters the unit, with fast stabilization of the AAI. The different extent of the AAI increase could not be related to any specific unit condition, maybe because the main steam parameters such as temperature (680-720C) and partial pressure (20-30%) were approximately the same for all cases. Catalysts, especially depending on technology, are more or less susceptible to this effect. In the opposite direction, of reducing AAI, the only possible cause relies on the sintering effect caused by contaminant metals, under more and less severe FCCU conditions. This is certainly the dominant mechanism responsible for the AAI loss in several cases reported in literature. However, in the present study, only iron has been found as possible candidate to cause AAI decrease. Temporary iron contamination in Brazilian RFCC units proved that accessibility could be dramatically reduced due to pore blocking of the outer surface. Contaminants like nickel, vanadium and sodium showed negligible effect on accessibility if compared to iron. A mental model based on these two opposite driving vectors steaming and metal deposition was used to explain the different possibilities of catalyst accessibility behavior in the FCC unit. Commercial experience in Petrobras demonstrated that application of high accessibility catalysts were advantageous, even for some units not processing residue. The monitoring of E-cat accessibility, as measured by the AAI test, has recently become a routine for RFCCs in Petrobras and is highly recommended for any FCCU that operates in diffusion-limited regime.

References
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3. 4. 5. 6. 7. 8. 9. 10. 11. 12. Torem, M.A.; PACRC - Um Marco no Processo de Craqueamento Cataltico Fluido. IV Encontro Sul-Americano de Craqueamento Catalitico, Manaus, Brazil, August, 2000 p.91. Leite, L.F., Scholosser. C.R., Ramos, J. G. F. and Yung, K.Y.; Synergy effect of improved accessibility catalysts . REFINING PTQ Spring, 37 - 43, 2000. Morgado, Jr.,E , Leite, L.F., Pravia, O.C. and Torem, M.A., New and Improved Residue FCC catalyst. Hydrocarbon Engineering, January, 2002. McLean, J.B.; Stockwell, D.M., Naphtamax TM Breakthrough FCC catalysts technology for short contact time applications. NPRA 2001 Annual Meeting, New Orleans, March 2001. OConnor, P., and Humphries, A., Accessibility of functional sites in FCC, ACS preprints, vol. 38, no. 3, p. 598, 1993. Boot, L.A., Boer, M. de, Desai, P.H., and OConnor, P., Hydrocarbon Engineering, p.59, September 1998. Humphries, A., Fletcher, R.P. and Pearce, J. A unique development in FCC catalyst technology maximizes refinery profitability. NPRA Annual Meeting; March, 1999. Kuehler, C.W., Jonker, R., and OConnor, P., The influence of fresh and contaminant-affected catalyst structure on FCC performance, IV Encontro Sul-Americano de Craqueamento Catalitico Manaus, Brazil, August, 2000, p. 199. Hakuli, A.K., Imhof, P. and Kuehler, C. Understanding FCC catalyst architecture and accessibility. Akzo-Nobel Catalysts Symposium ECO-Magic; The Netherlands, June, 2001. Yanik, S.J., Humphries, A. and Fletcher, R.P. Inventing the future in RFCC: Jadeand Topaz technology. Akzo-Nobel Catalysts Symposium ECO-Magic; The Netherlands, June, 2001. Morgado, Jr.,E , Almeida, M.B.B. and Torchio, R.O..; Catalisadores de Craqueamento de Alta Mesoporosidade. Rio Oil&Gas Expo and Conference 2000, Rio de Janeiro, Brazil, October, 2000. Kuehler, C.W., Jonker, R., Imhof, P., Yanik, S.J. and OConnor, P., Catalyst Assembly Technology in FCC. Part II: The influence of fresh and contaminant-affected catalysts structure on FCC performance. In: Ocelli, M.L & OConnor, P. (ed.), Fluid Catalytic Cracking V. Materials and Technology Innovations, Studies in Surface Science and Catalysis, Elsevier, 2001. Fletcher, R.P., Hakuli, A.K. and Imhof, P. FCC catalyst selection in diffusion limited operating rd regimes. 3 European Catalyst Technology Conference; Amsterdam, February, 2002.

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14. Almeida, M.B.B. Internal Technical Report TFCC 02/2002, Petrobras / R&D Center; January 2002. 15. OConnor, P., Imhof, P. and Yanik, S.J. Catalyst Assembly Technology in FCC: A review of the concept, history and developments. ACS preprints, 1999, 44 (4), 466-472. 16. Kampen, J. Separation of FCC catalyst on skeletal density. R&D method internal report, AkzoNobel; March 1997. 17. Yaluris, G., Cheng, W., Peters, M. Boock, L.T. and Hunt, L. The effects of iron poisoning on FCC catalysts. NPRA Annual Meeting; New Orleans, March, 2001. 18. Rainer, D. et al. to be published. 19. Wieland W.S. and McLean J.B. Impact of contaminant iron on FCC catalyst performance. 3rd European Catalyst Technology Conference; Amsterdam, February, 2002. 20. Hodgson, M.C.J., Choo Kiong Looi, Yanik, S.J., Avoid Excessive RFCCU Deactivation Improve Catalyst Acessibility, Akzo Nobel Catalysts Symposium 1998.

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