The GENESIS TM Catalyst System

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1 The TM Catalyst System Rosann K. Schiller Product Manager Denise Farmer Senior R&D Engineer Larry Langan R&D Engineer Grace Davison Refining Technologies Columbia, MD M ost refiners need flexible catalyst systems that allow them to take advantage of changing operating situations and feedstocks. Grace Davison delivers this flexibility with the catalyst system. catalysts provide a means to maximize yield potential through the optimization of discrete cracking catalyst functionality. catalysts are a blend of two catalyst types in which one component is a catalyst. The GENE- SIS blend concept requires that each catalyst component excel in specific performance categories in standalone use. The component provides a high matrix input, maximizing conversion of bottoms and increasing LCO yield in many operating scenarios. Designed for refiners who are interested in maximum bottoms upgrading, offers the ultimate in bottoms destruction and catalyst stability [1] without a coke or gas penalty, as often has been seen with competitive high matrix catalysts. The other component is usually a high zeolite containing catalyst and is most often an catalyst. The family has been a breakthrough in catalytic cracking. [2,3,4,5] The novel, integral rare earth based vanadium-trapping technology in delivers Catalagram 102 Fall 200 3

2 exceptional activity maintenance, coke and gas selectivity. The inclusion of in the system provides critical zeolite surface area and activity as well as superior coke and gas selectivity in a broad range of applications, from severely hydrotreated gasoils to heavy resid feeds. It is well known that the key to optimal FCC catalyst performance is the right balance between zeolite activity and matrix activity, or the Z/M ratio. [6] In pilot plant comparison testing, a high Z/M catalyst will tend to have better coke and gas selectivity than a low Z/M formulation. However, the low Z/M catalyst will achieve lower bottoms yield at constant conversion, often with a coke penalty. It is critical that zeolite and matrix activity are appropriately balanced for each unit, taking into consideration the type of feed that is processed along with the unit constraints and objectives. The GENE- SIS concept provides the ultimate in flexibility to optimize formulation Z/M for each specific application. : The Key Component The superior bottoms destruction and catalytic stability obtained from its open particle morphology make an excellent fit for application in all units wishing to minimize slurry. Moreover, the design of this catalyst maximizes the balance of pores in the Å range with an optimized ratio of weak to strong acid sites in the matrix. This balance of mesoporosity and optimized acid strength greatly improves the selectivity of the bottoms cracking reactions that take place without the gas penalty often observed with other high matrix catalysts. [3] For short contact time FCC applications, it is critical that feed molecules have no limitations in getting to the catalyst acid sites, and the catalyst architecture is ideal for eliminating diffusion constraints. [] In addition to overcoming the challenges of diffusion limited systems, catalysts are also 4 Hydrogen, wt.% Figure 1 Commercial Performance Competitive Low Z/M Catalyst Figure 2 Commercial Performance Competitive Low Z/M Catalyst Conversion, wt.% Table I Properties of and Catalysts Fresh Properties Al 2 O 3, wt.% Re 2 O 3, wt.% Surface Area, m 2 /g Zeolite, m 2 /g Matrix, m 2 /g Deactivated Properties Surface Area, m 2 /g 1 15 Zeolite, m 2 /g Matrix, m 2 /g 3 3 Unit Cell, Å Hg PSD, cm 3 /g , cm 3 /g , cm 3 /g , cm 3 /g

3 Conversion, wt.% designed to minimize the deleterious effects of high equilibrium catalyst (Ecat) contaminant metals levels associated with resid processing while delivering superior bottoms cracking to LCO and gasoline at low coke yield. The benefits of the architecture have been demonstrated in commercial applications. Figures 1 and 2 compare the performance of to a competitive high matrix catalyst technology. Not only does demonstrate excellent bottoms cracking, it also reduced hydrogen production by 20% despite higher metals on Ecat. : Combined Effectiveness Figure 3 DCR Evaluation on Resid Feedstock Bottoms Selectivity exists and catalysts demonstrate a superior coke to bottoms relationship than either component alone. The synergy is attributable to the unique matrix properties of and its interaction with Grace Davison high zeolite catalyst technology. This synergy is the greatest when is combined with the catalyst family; however similar performance advantages are seen when is combined with other high zeolite Davison catalysts. Grace Davison has done extensive R&D work to understand the synergy that exists between and. The summary of that data is presented here. Table II Properties of Feedstocks Research & Development Traditionally, in testing, the expectation of catalyst blend performance is that the resultant yields would be close to the linear average of each individual catalyst. In performance testing of systems, the resultant yields exceed those of either blend component. A comprehensive study was designed to measure the selectivity advantage of these catalyst systems due to the synergy that exists between and. Properties of commercially produced and catalysts are shown in Table I. The catalysts were deactivated individually using the CPS-3 protocol [9] at 1465ºF, and the blend was prepared after the steaming of each component. The two catalysts had similar unit cell sizes after steaming. had lower zeolite and higher matrix surface area with higher pore volume. The catalysts were tested in the Davison Circulating Riser (DCR) on a resid, a VGO, and a hydrotreated VGO feedstock. The properties of the feedstocks are shown in Table II. The resid feed has 5.1 wt.% Con Carbon, 20.6 ºAPI and about 35% 1000ºF+. The VGO feed is paraffinic (11.94 K-Factor) with about 15% 1000ºF+. The hydrotreated feed has very low sulfur (0.035 wt.%) and is highly naphthenic (3.2% Cn). Since is the key component in the blends, the expectation is that the bottoms cracking performance of the system would be improved over alone. Generally when bottoms cracking increases, there is a decline in coke selectivity and vice versa. It is expected that as matrix activity increases this is also true. [] However, the relationship between bottoms cracking and coke selectivity of the system is unique in that increased bottoms cracking is accompanied by improved coke selectivity. A synergistic effect Resid Feed VGO Hydrotreated VGO API F Sulfur, wt.% Conradson Carbon, wt.% Ni, ppm V, ppm K Factor Refractive Index Average Molecular Weight % Paraffinic Ring Carbons, Cp % Naphthenic Ring Carbons, Cn % Aromatic Ring Carbons, Ca Simulated Distillation, vol.%, F IBP % % % % % FBP Catalagram 102 Fall 200 5

4 Figure 4 DCR Evaluation on Feedstock Coke Selective Bottoms Cracking The yields on the resid feedstock (Table III, Figure 3) show that at constant conversion, produced about 0. wt.% lower bottoms than. However, had lower coke and produced only 0.25 wt.% higher bottoms than. has a bottoms yield lower than that of the weighted average of the and and a coke yield similar or better than. Overall, had the lowest bottoms at constant coke (Figure 4). Remarkably, this phenomenon is observed across a broad range of feeds, e.g. VGO feed (Table IV, Figures 5-6) and hydrotreated feedstock (Table V, Figure -). 6 Table III DCR Evaluation Resid Feedstock Constant Conversion Comparison Since and crack different molecules in the feed, these analyses reveal the strength of the approach. is more effective at cracking the parafwww.e-catalysts.com Cat to Oil...5 Total Dry Gas, wt.% H 2 Yield, wt.% Total C 3, wt.% Total C 4, wt.% Gasolin e, wt.% LCO, wt.% Figure 5 DCR Evaluation Bottoms Selectivity VGO Feedstock Conversion, wt.% Evidence of Synergy The detailed simulated distillation data of the bottoms (650ºF+) fractions from the DCR study are shown in Figures For the resid and VGO feedstocks, excels at cracking the lighter (650-50ºF) bottoms, while is superior in cracking the heavier ( ºF) bottoms. For the hydrotreated feed, both the and completely destroy the 900ºF+ portion of the bottoms. was the most effective in cracking bottoms of all boiling ranges for this highly naphthenic feed. [10] The 650ºF+ yield from the DCR pilot plant was separated by the clay/gel method and analyzed by GC mass spectrometry [ASTM D26-91 and D ]. The analyses for the resid and hydrotreated feeds are shown in Figures 12 and 13. is most efficient in cracking the paraffins and single ring naphthenes. and were more effective in cracking the 2-4 ring naphthenes. These data reflect the selectivity shown in Figures 9 and 11.

5 fins and the lower-boiling fraction of the feed, while is more effective at cracking the naphthenes and the higher-boiling fraction of the feed. The blend is tailored in all cases for the specific feedstock type. Why It Works catalysts optimize the three-step bottoms cracking mechanism of Zhao et. al. [10], shown in Figure 14. Type I cracking involves vaporizing the feed. Since resid feeds may contain a significant amount of molecules boiling above the mix zone temperature of the riser (ca. 100ºF), pre-cracking, either catalytic or thermal, is necessary to achieve complete vaporization. Depending on the atomization efficiency, vaporization time of resid feed droplets may approach that of the riser contact time, which may lead to bypassing of the feed through the riser. [11] High porosity in the range of 100 to 600 Å, a signature of (Table I), is particularly effective for adsorbing and facilitating the coke-selective cracking of large molecules during this stage. Type II cracking, involving dealkylation and paraffin cracking, is readily catalyzed by high zeolitic activity catalysts, such as. The Type III mechanism involves cracking the naphthene rings of naphthenoaromatic compounds. These reactions are more demanding, as the competing aromatization reactions (hydrogen transfer and dehydrogenation) proceed readily. selectively cracks the naphthene rings without any coke or gas penalty. Current Worldwide Use The synergy we observe in laboratory testing has easily translated to field performance. Figure 15 illustrates the performance advantage observed in commercial testing. The data presented here are three commercially deactivated Ecats taken from an FCC unit pro Figure 6 Coke Selective Bottoms Cracking DCR Evaluation on VGO Feedstock Table IV DCR Evaluation VGO Feedstock Constant Conversion Comparison Cat to Oil Total Dry Gas, wt.% H 2 Yield, wt.% Total C 3, wt.% Total C 4, wt.% Gasoline, wt.% LCO, wt.% Figure Bottoms Selectivity DCR Evaluation on Hydrotreated Feed Conversion, wt.% 4 5 Catalagram 102 Fall 200

6 cessing resid that has used and separately as well as a blend of both technologies. These Ecats were then tested in an ACE pilot plant over a single feed. has the advantage in coke-selective bottoms cracking. For resid applications, blends allow for maximization of carbon content of the feed or increased conversion up to the coke burn limit Figure DCR Evaluation on Hydrotreated Feedstock Coke Selective Bottoms Cracking We've demonstrated how performs relative to the individual components, but how does GENE- SIS compare to other technologies? A refiner processing hydrotreated feed switched from a state-of-theart Davison catalyst for hydrotreated feeds to a system comprised of and. Figure 16 demonstrates the performance advantage of relative to the hydrotreated benchmark technology. In ACE testing of unit Ecats, results in an improved coke-to-bottoms relationship, providing the ultimate in operating flexibility for this refiner to optimize hydrotreating and FCC operations. In catalysts, typically the other blend component is from the family. The full range of Davison Al-Sol and Si-Sol catalysts have been used with success in systems as shown in Table VI. These commercial applications demonstrate the viability of the catalyst system across many different feed types. Conclusions Table V DCR Evaluation Hydrotreated Feedstock Constant Conversion Comparison Cat to Oil... Total Dry Gas, wt.% H 2 Yield, wt.% Total C 3, wt.% Total C 4, wt.% Gasoline, wt.% LCO, wt.% Figure 9 Bottoms Cracking Selectivity Resid Feedstock Constant Conversion DCR Comparison In the DCR study, we saw that the system consistently performs with the coke selectivity of and the bottoms selectivity of, yielding the synergistic effect of a superior coke-to-bottoms relationship. This synergy exists because both catalysts crack specific feed species: cracks paraffins more efficiently while destroys more ringed naph- Yield, wt.% of Feed is more selective in cracking the heaviest fraction of the feedstock Boiling range F

7 Yield, wt.% Figure 10 Bottoms Cracking Selectivity VGO Feedstock Constant Conversion DCR Comparison Boiling range F Figure 11 Bottoms Cracking Selectivity Hydrotreated VGO Feedstock Constant Conversion DCR Comparison Yield, wt.% Boiling range F thenes. improves unit coke selectivity by effectively eliminating and cracking coke precursors. The system provides the utmost in formulation flexibility by custom tuning the blend ratio. We can optimize the catalyst Z/M ratio to match the specific unit feedstock and operating constraints. In addition to optimizing the blend ratio, the activity levels of the individual components are carefully selected to match the operating mode and feed types. This formulation flexibility can deliver a significant selectivity change, allowing the refiner to accommodate a seasonal operation, or to manage a swing feedstock, or even a hydrotreater outage. In high metals resid applications, catalysts allow for maximization of carbon content of the feed or for increased conversion up to the coke burn limit. Not only does reduce slurry yield, it does so without the expected coke and gas penalty often observed with competitive high matrix catalysts. In VGO and hydrotreated feed applications, provides operational flexibility to react to seasonal economics and the opportunity to optimize hydrotreater and FCC operations together Figure 12 GC/MS Characterization of Bottoms Resid Feedstock Constant Conversion Comparison For more information on how GENE- SIS catalysts can improve your operation, please call your Grace Davison Sales Representative or Rosann Schiller at (410) , rosann.schiller@grace.com wt.% of Bottoms Paraffins 1-Ring 2-Ring 3-Ring 4-Ring Catalagram 102 Fall 200 9

8 Figure 13 GC/MS Characterization of Bottoms Hydrotreated Feedstock Constant Conversion Comparison wt.% of Bottoms Paraffins 1-Ring 2-Ring 3-Ring 4-Ring Figure 14 Bottoms Cracking Mechanism Catalytic Type II R Type III R Type I Coke Feed Thermal/Catalytic is more effective for Type I and Type III. is more effective for Type II. 9 Figure 15 Commercial Resid Example of Synergy

9 Name Table VI Applications Ni + V Feed Type Blend Component Refiner 1 25 VGO SPECTRA Refiner Hydrotreated Refiner Hydrotreated ORION Refiner Hydrotreated Refiner VGO Refiner VGO Refiner 100 VGO Refiner 1900 VGO Refiner Resid AURORA Refiner Resid Refiner Resid SPECTRA Refiner VGO ORION Refiner VGO Refiner Resid Refiner VGO AURORA Refiner VGO Refiner Resid Refiner Resid Refiner Resid AURORA Refiner Resid ORION Refiner Resid Refiner Resid Refiner Resid ADVANTA Refiner Resid Refiner Resid Figure 16 Outperforms Benchmark Catalyst for Hydrotreated Feeds ECAT ACE TESTING 11 References 1. Catalagram 9, Maximizing Bottoms Upgrading: Give Resid the TM Touch, Hunt, L., Fall Catalagram 93, TM : A Breakthrough Technology for Resid Processing - Commercial Update, Purnell, S.K., Fall Catalagram 96, New Catalyst Technologies Based on Tunable Reactive Matrices: TM, LIBRA TM and POLAR- IS TM, Cheng, W.C. & Nee, J.R., Fall Catalagram 9, Next Generation Al- Sol FCC Catalyst Technologies, Nee, J.R., Spring Catalagram 99, Recent Commercial Experience in Improving Refinery Profitability with Grace Davison Alumina-Sol Catalysts, Petti, N., Yaluris, G., Hunt, L., Spring Mott, R.W., Wear, C., FCC Catalyst Design for Optimal Performance, NPRA Annual Meeting 19, AM--3.. Spry, J.C., Sawyer, W.H., 6th Annual AIChE Meeting, Los Angeles Young, G.W., Creighton, J., Wear, C., Ritter, R.E., Effect of Feed Properties on the Optimization of FCC Catalysts for Bottoms Reduction. NPRA 19, Annual Meeting, AM Wallenstein, D, Harding, R. H., Nee, J. R. D., Boock, L. T.; Recent Advances in the Deactivation of FCC Catalysts by Cyclic Propylene Steaming (CPS) in the Presence and Absence of Metals; Appl. Catalysis A: General 204 (2000) Zhao, X., Cheng, W-C., Rudesill, J. A.; FCC Bottoms Cracking Mechanisms and Implications for Catalyst Design for Resid Applications ; NPRA Annual Meeting, San Antonio, TX, Huang, Z., and Ho, T. C.; Effect of Thermolysis on Resid Droplet Vaporization in Fluid Catalytic Cracking; Chemical Engineering Journal, 91 (2003) Grace HT Benchmark Catalagram 102 Fall

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