FUTURE OF FCC AND RECOMMENDATIONS FOR RESEARCH ‘This section summarizes speculation on the future of FCC and recommendations for research found throughout Parts 1 and 2 of this study. Although priorities vary, typical FCC researchers aim to improve: + Gasoline yield + Octane yield + Resid cracking ‘+ LCO conversion and quality + Catalyst performance and attrition resistance + Metal management technology + Reactor technology + SOcand NOx emissions contro! * Long-term prospects for the petroleum industry 51 GASOLINE YIELD ‘The major market for refined petroleum in the US. is automotive fuels, which is dominated by gasoline, Diesel-powered vehicles gained popularity in the late 1970s and early 1980s, but they have not penetrated the market significantly. The replacement of older, less fuel-afficient vehicles by new models has lowered the rate of increase in transportation fuel demand; however, estimates of total annual miles driven are rapidly increasing. This suggests that without further perturbations, gasoline demand should begin to increase and parallel the annual mileage increase. To meet this demand, more gasoline will be needed. ‘ Simulataneously, the options available to refiners to provide product to satisfy this demand have decreased. The use of lead aditives to increase octane value is no longer possible in the U.S. To maintain the octane level, the refiner must accept lower gasoline yield, install additional processing ‘units to increase octane, or purchase octane boosters. Meanwhile demand for heavy refinery byproducts that are not amenable to upgrading decreases, and restrictions on the amounts of high-octane, high-vapor-pressure gasoline components, such as butanes, have been proposed. 307Strategies to maximize the benefit from the light and heavy ends of the refinery are crucial to a plant's profit. ‘The trends in Europe and Japan will likely parallel the U.S. experience, although the time seale will Giffer and special conditions will likely occur in certain geographic areas. Buropean and Japanese refiners can use the U.S. experience to identify successful answers and avoid potentially disastrous approaches to these challenges, ‘The refiner who can best predict future product demand and catalyst performance, and therby configure a refinery that maximizes profit earned from the product streams, will survive, Demand and profit are hard to forecast, but catalyst performance at different reactor conditions can be quantified. 52 OCTANE YIELD Higher reactor temperatures produce more gasoline, less LLCO, and improve the octane number. A different eatalyst ean also increase octane. Preferred octane enhancing catalysts are USY and framework silieonenriched zeolites. These zeolites are expensive, yet the drive to produce them in larger quantities and at lower cost is, and will remain, strong, as will the drive to explore cheaper alternatives, For instance, researchers are currently testing less expensive alternatives such as alumina-impregnated ¥ zeolite and partially rare earth-exchanged ¥ zeolite, Shape-selective zeolites such as ZSM-5 enhance octane by selectively cracking low-octane components to liquefied petroleum gas. Accompanying the octane gain, however, is a few percent loss in gasoline yield. These costly catalysts have not yet been widely adopted for commercial FCC, but increased processing of recalcitrant feedstocks and greater octane demand should increase their use. As patents expire, these catalysts should become cheaper and more available. To date, octane enhancers are often only partially effective; they improve RON, not MON. To improve ‘MON, the feed should contain more isomeric branched paraffins, which means that the cracking catalyst should also catalyze isomerization. An alkylation unit ean also ill the need for isoparaffins if the supply of branched olefins is sufficient, Alkylation is extensively practiced in the U.S. but not in other countries, because product demands and economies are different. As product demands evolve, non-US. refineries may have to seriously consider adopting alkylation technology. Other methods of octane boosting available to refiners include blending oxygenates, such as MTBE and GTBA (methyl t-butyl ether and gasoline grade t-butyl alcohol), dehydrogenation, and isomerization. Some of these options may be more expensive than others, so their various economics must be carefully compared. It is important to note that a recent plant accident may have an impact on future refinery operations. Late in 1987 an HF alkylation unit in the southern U.S. experienced an upset, Serious concerns about the safety of H-catalyzed alkylation units are now being voiced, This attention eould lead to legislation that restricts or forbids the use of HF and that promotes the the use of safer acids, perhaps zeolites. Legislated restrictions on HF (or HyS0,) alkylation units would seriously decrease the available octane barrels. 3085.38 RESID CRACKING 5.3.1 Asphaltenes ‘The key issue in resid processing is the cracking of bottoms molecules, especially asphaltenes, but the mechanism is poorly understood. Asphaltenes have been extensively studied in connection with hydrotreating, and the basie principles should apply to FEC. Although coal-derived asphaltenes are different from petroleum asphaltenes, coal liquefaction studies may also provide information valuable to FCC. Ideally, when an asphaltene molecule contacts a hot regenerated catalyst particle, the asphaltene shatters into fragments that the catalyst matrix further cracks into molecules small enough to diffuse through the zeolite pores. The shattering and subsequent matrix cracking of the asphaltene fragments should occur rapidly and are perhaps the most critical steps in resid cracking. ‘Understanding how these key steps occur at the molecular level and how to control them, is essential to efficient resid cracking that maximizes the yield of useful products and reduces deactivation by coke deposition. Convenient analytical methods to follow the course of the asphaltene cracking should be devised and widely adopted. Low-sadium zeolite catalysts such as USY cope more effectively with resid processing and its associated problems than catalysts containing more sodium. Shape-selective catalysts are of litle ‘use in resid cracking because the resid molecules are too large to enter into the zeolite pore: Consequently unselective surface cracking predominates, although some of the surface-cracked products can enter the zeolite pores and undergo further conversion. 5.3.2 Low-Cost Resid Cracking Catalyst Resid cracking can require inordinate amounts of fresh catalyst to cope with heavy metals, contamination, Thus a low-cost, relatively active, and selective catalyst would be a boon to the industry. Currently refiners must weigh the benefits of an active, selective, and expensive catalyst that quickly loses activity and selectivity due to metals poisoning against a cheaper catalyst that is less active or selective and less susceptible to metals poisoning. 5.3.3 Resid Prospects ‘The oil crises stimulated cil exploration and energy conservation, which, in turn, created en energy surplus. However, as in the early 1980s, the crude supply is expected to tighten in the future and push prices up. Crudes will grow heavier (as lighter crudes are produced first), which will inerease the residual portion of erude and again raise the question of what to do with the resid. Marketed as residual fuel oil, resids would compete against low-cost primary fuel sources such as natural gas and coal and alternative fuel sources such as nuclear and sclar energy. Unable to compete economically, resid fuel oils would undoubtedly lose their market share as they did in the late 1970s and early 1980s. Clearly, refining flexibility will once again be the key to refinery viability 309Over the last 20 years, when resid fuel ofls failed to compete against primary fuels, FOC resid conversion capability developed impressively, Although current FCC development focuses on octane enhancement, the future is clear and efforts are being made to increase resid handling capabilities, Among the refining processes, FCC is perhaps the best suited to resid upgrading. Flexicoking and hydrocracking are FCC's major competitors, but they are costly to build and operate and not Likely to grow at FCC's expense, Hydrotreating is not a competitor but an ally. It pretreats highly contaminated resids and renders them suitable for FCC, In the future, however, efficient resid crackers may process resids of increasing contaminant level, as we have already seen. 5.3.4 Hybrid Resid Crackers Hybrid units such as those employed in the ART, MRS, and RAROP processes are better classified as. resid pretreaters rather than crackers. Hybrid cracker technology is based on the premise that Pretreatment with low-cost solids such as kaolin, neutralized equilibrium catalyst, and powdered Sron ore removes metals and coke precursors in resid, As an alternative ta salvent deasphalting, hybrid resid cracker technology will likely gain commercial acceptance. 5.4 LCO CONVERSION AND QUALITY ‘To date, most FCC innovation has been directed toward increased conversion to gasoline and to processing of heavier, marginal feeds. Light cycle oil, a principal component of No. 2 fuel oil and . diesel fuel, has been considered a secondary product; in fact, itis generally excluded from FCC conversion calculations. Although the relative yield is lower, LCO commands almost the same price as gasoline (Obel, 1986a), therefore it should be ranked equally in FCC economies. Because demand for diesel fuels will Continue to increase, the importance of LCO in U.S. FCC economies will also increase, coming inte line with Europe and Japan, where LCO is much more highly regarded. ‘High-octane catalysts based on USY produce poor quality LCO compared with that produced by REY catalysts. Increasing FCC operating severity to produce high-octane gasoline negatively affects LCO quality. Catalytic and technological advances are yet to come. 5.5 CATALYST PERFORMANCE AND ATTRITION RESISTANCE 5.5.1 Blended Catalysts Blended catalysts offer a higher degree of customization, and today’s FCC catalyst supply service is moving in that direction. Katalistiks’ BMZ eatalyst series and Engelhard’s Dynamics series are representative of this trend, Bach series blends multiple components to create near-custom catalysts, ‘Multifunctional preparations comprising high- and low-activity catalysts or large and small particles blended from two or more different manufacturers’ product lines would further enhance 10customization. High-activity low-sodium zeolites such as USY or other active zeolites such as caleined REY could be added in the same particles or in separate particles. The matrix would consist of clay, possibly coated to impart desired properties, and a binder for hardness and attrition, resistance. The matrix, which might also show cracking activity, should complement the matrix of the low-activity fraction, The low-activity fraction would, for example, consist of clay, possibly coated and bound for maximum hardness, and special components that impart functions not included in the high-activity fraction, such as: = SOx contro! + CO combustion ‘© Metal passivation + Paraffin isomerization + LCO yield enhancement New Catalytic Materials Current developments in FCC catalysts are not as dramatic as the introduction of zeolitic cracking catalysts. However, a major breakthrough involving new materials cannot be discounted. These new and improved materials wil likely be microporous erystalline materials or layered structures. Work 4s progressing on the synthesis of titanium and zirconium silicates, although none show particular promise, Pillared clays may become important if thelr hydrothermal stability ean be improved. 5.5.3. Attrition Resistance Powerful operational, economic, and environmental forces drive the development of attrition resistant catalysts. Catalyst manufacturers all like to claim their catalysts are the hardest in the industry because, everything else being equal, customers always choose the hardest catalyst. New or improved binders and improved manufacturing methods are needed. 5.5.4 Catalyst Research FCC catalyst researchers work continually to improve catalyst performance. Hettinger (981) suggests that the perfect FCC eatalyst would completely redistribute the feed hydrogen and carbon ‘to our liking and would produce a mixture of two very high octane hydrocarbons, toluene and isooctane, with volume yields in the 125 to 140% range. Obviously, there are technical barriers to such a catalyst, but this gives us a glimpse of future possibilities for heavy oil upgrading. New ultrastabilization techniques produce high-stability zeolites (USYs having little amorphous silica-alumina debris and few crystallographic defects). These zeolites are much cleaner than USYs prepared by conventional high-temperature steaming or by chemical means. The new method of USY synthesis brings the industry one step closer to molecularly designed catalysts and Hettinger's ideal. aul‘The next area to focus on is active site characterization, Knowing the acid strength, cationic site distribution, and pore size distribution would help answer the question of how ta increase MON along with RON. 5.6 METAL MANAGEMENT TECHNOLOGY 5.6.1 Metal Passivation Passivation of nickel contaminants on FCC equilibrium catalysts is a fairly well established technology; vanadium passivation is not. The technology urgently needs improvement because octane-boosting catalysts are susceptible to contaminant metals deactivation, and FCC feeds contain increasing amounts of metal contaminants, Refiners prefer passivation because it is more direct and expedient than demetallation, In contrast to the average metals level on equilibrium catalysts (3,000 ‘0 6,000 ppm), some experimental catalysts reportedly tolerate as much as 20,000 ppm metals. Future research should target several fertile areas, including: ‘+ Incorporating passivation components in the catalyst + Manipulating catalyst manufacturing conditions (manipulating physical properties or using special activation techniques) ‘Blending catalyst components ‘+ Using special additives in feed or in fresh catalyst * Creating regenerator or reactor conditions amenable to metals passivation 5.6.2 Metal Conditioning On every cracking cycle, heavy metals, vanadium and nickel, deposit on the catalyst, Dehydrogenation activity is highest for the freshly deposited metals and declines with each succeeding regeneration cyele . Although the phenomenon has been recognized for some time, the ‘mechanism is not well documented. Understanding the mechanism would lead to vastly improved metals passivation technology. Some developments exploit the fact that metals deactivate under certain conditions. In a process called catalyst conditioning, for example, UOP’s RCC unit injects a mixture of light hydrocarbons and steam at the base of the riser to passivate metals on the eatalyst, The mechanisms responsible are not clear, Metals conditioning is beneficial to resid eracking because heavy feeds inherently contain higher amounts of metals. The concept deserves further exploration. 125.6.3 Demetallation As the industry increases use of more expensive, metal-sensitive octane catalysts based on ultrastabilized or silicon-enriched zeolites, demetallation of eontaminated FCC catalyst may make economic sense. The subject is also timely because FCC feed contamination will inerease as crudes become heavier and dirtier, FCC catalyst demetallation is not currently practiced, but efforts are being made to develop removal techniques for three target metals: sodium, vanadium, and nickel. Sodium, which destroys the zeolite lattice, is easily removed by ion exchange, Removal of vanadium and nickel still involves multistep treatments, Some new technologies have reached the demonstration stage; commercialization mostly hinges on economies, and economic incentives are expected to increase. 5.7 REACTOR TECHNOLOGY ‘The benefits associated with increasing the cracking temperature, such as higher gasoline octane and lower coke make, are well known. Experiments indicate that coke make drops precipitously as cracking temperature increases and residence time decreases, until only a trace amount is formed er cycle above 620°C (1148°R). Unfortunately, under these conditions, thermal eracking rises sharply unless residence time is further reduced. At a cracking temperature of 620°C, a contact time on the order of 100 ms is required. This is beyond the capability of eurrent reactor technology. Nevertheless, the low coke make in high-temperature short-contact cracking is appealing. Present FCC reactor designs feature an average contact time of a few seconds or more. Clearly, these are not suitable for short-contact cracking, New developments in reactor design that permit subsecond contact times are needed. Not only must the contact time be shortened, but the eatalyst disengagement time must also be shortened to minimize overcracking. An effective way to quench the hot products to avoid thermal cracking and polymerization of olefins and polyaromatics must also be found. Chen’s (1986e) recent bench-scale experiment demonstrates the feasibility and benefits of ultra-short-contact-time eracking. Using conventional FCC catalysts, gas oils crack at reasonable conversion, low coke meke, and increased RON. ‘This promising work brings FCC dloser to the realm of steam cracking where thermal activity dominates. Tt also raises many questions and suggests many avenues of possible development 5.8 SOx CONTROL In FCC a catalytic method for SOx control is considered the most economically and operationally desirable solution (McArthur, 1981b). An all-purpose SOx catalyst or eatalytic additive, upon development, could be sold at triple the price of conventional cracking catalyst and still be more cost effective than flue gas treatment. Current annual sales of SOx control catalysts or agents are only $15 MAM, but sales will double every year for the next several years (Chem. Week, 1985a), 313One of the most stringent SOx emission standards is set by the Southern California Coastal Air Quality Management District, which recently lowered its limit to 60 kg/1L000 bbl (132 lv1000 bbl). Ta provide a perspective, a 50,000 bpd FCC unit processing a feed containing 1.0 wt% sulfur emits 480 1i71000 bbl without SOx capture (Thiel, 1986b). To meet the new standard, such an FCC unit would have to reduce its emission by 73%. Several SOx catalysts or additives are available today. However, on average, current SOx catalysts and additives reduce SOx emissions by only 30 to 60%, the higher numbers reported under optimal conditions (Thiel, 1985b; Powell, 1986; Aitken, 1985). Obviously, these catalysts are not wholly satisfactory; improvements are needed, 5.9 LONG-TERM PROSPECTS FOR THE PETROLEUM INDUSTRY Cobb (1887) of Wright Killen & Co, bases his vision of the long-term prospects of the petroleum industry on the Kondratieff Long- Wave Cycle. According to this theory, a technological cycle begins with a decade of innovation followed by several decades of high investment and ends in a period of saturation and decline (Figure 5-1), Technologies that illustrate the principle include the steam engine and the railroad, Cobb's thesis is sensible and directly applicable to the petroleum industry. ‘The petroleum industry's period of robust growth appears to be aver because its driving foree, the automobile industry, is in the latter phase of a Long-Wave Cycle where growth is driven only by newly licensed drivers and the rate of replacement of existing cars. : REAL ECOMONIC GROWTH STAGNATION 3 Figure 5-1. Long-Wave Beonomic Cycle Reference: Cobb, 1987, audFigure 5-2 correlates U.S. petroleum consumption (the white line) with auto registrations (the black arog). Despite the continued increase in auto registrations into the 1990s, oil consumption is expected to decline. This reflects the fact that the auto and other petroleum-consuming industries shave increased their energy efficiency, and will continue to do so. Indeed any pressure toward higher petroleum prices, due either to increased demand or supply shortages, will be countered by increased energy efficiency. In the latter half of the technology cycle, an industry typically consolidates by closing inefficient plants, mergers, and vertical integration, Such changes have recently occurred in the U.S. petroleum industry. Between 1981 and 1985, more than 100 refineries, amounting to a crude capacity of almost 3.5 MMbpd closed. Of the shutdown refineries, 23% belonged to majors and 77% to independents, ‘The average refinery capacity was 61,000 bpd in 1981; in 1986 it was 79,000 bpd, indicating that larger refineries are viable, and smaller ones are closing. Although capacity in the petroleum industry has generelly decreased, conversion capacity has increased, signifying that the survivors of the competition are the most modern, sophisticated units with the highest conversion capabilities. Indeed, as cheap crudes disappear, FCG, a major conversion unit, faces a potential renaissance. ‘To be viable in the future, refiners must actively pursue: ‘+ Installation of modern control systems + Process and catalyst improvements Automobile Registrations Petroleum Consumptlons, (ations) (HM botaiday) 200 | Figure 5-2. Automotive Registrations and Petroleum Demand. SI Units: Reference: Cobb, 1987. = bbl x 159. 315* Debottlenecking + Increased energy efficiency + Environmental compliance + New processes ‘The message here is that petroleum refining and FCC will remain viable for years to come, but the ‘future is increasingly uncertain, Flexibility is central to viability in such an environment, and this is achieved only through innovations including increased computerization and catalyst research, 816