NEXT-LEVEL HYDROCRACKER FLEXIBILITY

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NEXT-LEVEL HYDROCRACKER FLEXIBILITY UNLOCKING HIGH PERFORMANCE IN TODAY S TURBULENT MARKETS WHITE PAPER

CONTENTS 1. POTENTIAL RESPONSES 5 1.1. Processing heavier, cheaper crudes 5 1.2. Processing non-standard feeds 5 1.3. Exploiting enhanced margins in lubricant base oils or petrochemicals 6 2. MAXIMIZING HYDROCRACKER FLEXIBILITY WITH INTEGRATED LINE-UPS 7 2.1. Enhancing the vacuum distillation unit (VDU) hydrocracker interface 7 2.2. Coker hydrocracker line-up 8 2.3. SDA hydrocracking line-up 9 2.4. Hydrocracking base oils line-up 10 3. CASE STUDIES 11 3.1. Hyundai s HVU hydrocracker base oils value chain 11 3.2. Grupa LOTOS unlocks the potential of DAO hydrocracking 13 4. KEY TAKEAWAYS 17 REFERENCE LIST 17 THE AUTHOR 18 ABOUT SHELL GLOBAL SOLUTIONS 18 3

NEXT-LEVEL HYDROCRACKER FLEXIBILITY: UNLOCKING HIGH PERFORMANCE IN TODAY S TURBULENT MARKETS John Baric, Licensing Technology Manager, Shell Global Solutions International BV As a critical catalytic conversion unit, the hydrocracker provides refiners with valuable feedstock and product slate flexibility. However, in recent years, several businesses have taken this flexibility to the next level. Some have adapted their units to handle extreme feeds, whereas others have transformed their operating strategies to capture new business opportunities in petrochemicals or lubricant base oils. In so doing, these refiners have unlocked some real performance differentiators and transformed the economics of their assets. The refining sector continues to experience volatile margins and an uncertain future. Even with the current low crude prices and reasonably healthy margins, the fuels commodities market is extremely competitive. The projected demands for traditional hydrocarbon fuel products such as gasoline, jet fuel and diesel continue to decline and the newly added, very-efficient refining capacity in Asia and the Middle East has increased competition. 4

1. POTENTIAL RESPONSES Among the numerous options that refiners can take to maintain or enhance their competitiveness, three are emerging that leverage the hydrocracker s flexibility. These are: processing heavier, cheaper crudes; processing non-standard feeds; and exploiting the enhanced margins in lubricant base oils or petrochemicals in some markets. 1.1. Processing heavier, cheaper crudes In recent years, many refinery schedulers and planners have been changing the crude diet. They have shifted away from the traditional Middle Eastern crude mix or Russian export blend to incorporate lowerpriced opportunity crudes such as West African, Mexican, Colombian and Venezuelan. However, compared with traditional, more easy-to-process grades, these present the refinery with several challenges because such crudes are typically high in: total acid number. With highly acidic crude, there is the risk of reliability issues and unplanned shutdowns, especially in the atmospheric and vacuum units. However, with appropriate controls on the crude blends, such problems can often be avoided with special metallurgy, inspection and corrosion monitoring programs, and corrosion-inhibiting chemicals. aromatics content. This puts pressure on distillate qualities and makes it more challenging to produce high-quality base oils. However, the combination of hydrocracking and distillate hydrotreating technologies has led to the development of sophisticated process configurations with catalysts applied specifically designed to reduce diesel density and aromatics, achieve substantial boiling point shift and improve cold flow properties, thus making the processing of high quantities of aromatic crudes possible. metals such as iron, nickel, vanadium, magnesium, sodium and calcium. These can cause serious fouling issues, but metals removal technology has made important advances recently. The proper selection and use of guard catalysts to ensure the protection of high-activity catalysts are vital. nitrogen. High nitrogen content puts pressure on the hydrocracker pretreat catalyst and may constrain hydrocracker capacity. The response from catalyst suppliers has been the co-development of much more active pretreat catalysts and cracking catalysts that have both higher activity and selectivity. This combination enables more reactor volume to be allocated to pretreat catalyst to handle the more difficult feed quality without significant loss of yield or cycle length. 1.2. Processing non-standard feeds Traditional hydrocracker feedstock such as straight-run vacuum gas oil (VGO) is now usually supplemented with cracked stocks originating from residue upgrading technologies such as delayed cokers, solvent deasphalters (SDA) and ebullated-bed and, in the near future, slurry-bed residue hydrocrackers. Such feeds, which include heavy coker gas oil (HCGO) and deasphalted oil (DAO), are more challenging to process, as they have much higher levels of contaminants such as nitrogen, Conradson carbon residue (CCR) and metals. Some also exhibit an inhibition nature through having already been cracked, which makes additional processing much more difficult. The availability and performance of the new generation of catalysts are key to enabling economic upgrading of these feedstocks, whether for a new hydrocracker design or a revamp of an existing hydrocracker. 5

1.3. Exploiting enhanced margins in lubricant base oils or petrochemicals Although middle distillates often provide a higher-value product stream, the economics in some regions are better for lubricant base oils or petrochemicals, and many refiners have been able to exploit them. In lubricants, this exploitation is partly driven by the transition in the base oil business from Group I products, based on solvent technology, to group II and III products based on catalytic dewaxing and hydrofinishing technology. A significant drop in demand for Group I products is expected, especially in Europe and North America, and there have already been several closures in Group I capacity in those regions. All the new base oil capacity and additional projects that have been announced are exclusively in groups II and III from catalytic technology. This is pertinent because group II and III base oils are typically derived from hydrocracker bottoms. Certainly, Group III requires the higher conversion that only a hydrocracker can provide for the required very high viscosity indices (VI) of 120 130. In short, the hydrocracker is critical because it will provide the feedstock for all future base oils. However, producing lubricant base oil feedstock requires in-depth understanding of what drives the properties of the unconverted material that comes off the bottom of the fractionator, especially the VI and aromatics, sulfur and nitrogen contents. Hydrocracker process configuration and the application of the right catalyst system are important to maximizing both the yield and the quality of the final base oil products. In petrochemicals, the historical feed for the ethylene cracker has been ethane. Of course, this is the best feed for producing ethylene, but supply is limited and plants have had to expand their feedstock range. Consequently, they have also used liquefied petroleum gas, naphtha, hydrotreated VGO and, recently, hydrocracker bottoms. Each time the feedstock gets heavier, the yield of ethylene falls and the amount of undesired residue increases, but of course the feedstock price is lower. As in refining, the petrochemicals sector experiences its own economic cycles and, when operating an integrated refinery petrochemicals business, the key to long-term success is feedstock flexibility. Hydrocracking has an important advantage here. Because it can put hydrogen selectively into the bottoms product, it can pull back some of the yield loss. The higher the hydrogen content, the higher the ethylene yield and the higher the value of this feedstock. Consequently, many modern ethylene crackers are being designed to process a wide variety of feedstocks, from ethane to naphtha to hydrocracker bottoms. The integration between the hydrocracker at Shell s Pernis refinery in the Netherlands and the nearby ethylene cracker at the Moerdijk petrochemical plant provides a case in point. When the hydrocracker was approaching the end of its cycle in 2013, the unit s technologists evaluated installing a new cracking catalyst that promised greater yields of high-value middle distillates. However, any such change could have had adverse effects on Shell s nearby Moerdijk petrochemicals facility, which co-processes hydrowax as a steam cracker feedstock (Figure 1). C4, naphtha, Jet A-1, ULSD LS VGO, Hycon VGO HS VGO, TCFD, Pernis FEU, HCO, XHGO Hydrowax FCC hydrocracker CC2 products Naphtha, LPG Moerdijk steam cracker MLO products FIGURE 1: HIGH-LEVEL BLOCK SCHEME SHOWING THE INTEGRATION BETWEEN THE HYDROCRACKER AND THE STEAM CRACKER. 6

If the new catalyst were to cause the hydrogen content of the hydrowax to decrease, the steam cracker s ethylene yield or the furnace s run length would be severely curtailed, so the technologists were keen to ensure that their new catalyst system could maintain the hydrowax quality and improve the middle distillate yield. Although taking such an integrated approach added substantial complexity to the catalyst selection process, post-project calculations showed that it enhanced the combined economics of the Pernis and Moerdijk plants by some $5 million a year. 1 2. MAXIMIZING HYDROCRACKER FLEXIBILITY WITH INTEGRATED LINE UPS This section examines some configurations that it is important to optimize to enhance the hydrocracker s contribution to the overall refinery margin. 2.1. Enhancing the vacuum distillation unit (VDU) hydrocracker interface The first step in any residue conversion scheme is to maximize the amount of VGO supplied by the VDU to the hydrocracker. This provides additional easy-to-process hydrocracker feed and enables the use of a smaller residue upgrader, thereby reducing the capital cost. Experience shows that, with the latest-generation separation technologies, it is often possible to go deeper into the vacuum residue and extract more VGO that is still within the hydrocracker s acceptable limits of heavy metals (vanadium and nickel), CCR and most important, C7-asphaltenes. For example, a refiner recently commissioned a VDU revamp, primarily to increase the feed rate to its hydrocracker and extend the VDU run length in-between decoking. As shown in Figure 2, the modifications required were relatively small, so were carried out during a routine refinery maintenance turnaround. Off-gas to vacuum ejectors New spray distributor LVGO New wash-oil bed structured paking HVGO New insulated double deck draw-off tray Atmospheric residue New stripping trays Steam Vacuum residue to visbreaker unit FIGURE 2: THE MODIFICATIONS TO THE VDU INCLUDED FITTING A NEW SPRAY DISTRIBUTOR, NEW WASH-OIL BED STRUCTURED PACKING AND NEW STRIPPING TRAYS. 1 According to 2013 economics and product pricing 7

As shown in Table 1, the revamp increased VGO recovery by about 2%. In addition, it helped to increase the VDU cycle length from three to four years. The capital cost was relatively low and the simple payback time was less than a year. VDU PRODUCTS PRE-REVAMP INTAKE YIELD, % WEIGHT ON FEED POST-REVAMP INTAKE YIELD, % WEIGHT ON FEED Offgas and slops 0.1 0.1 Light VGO 19.9 16.9 Heavy VGO 32.7 37.6 Total VGO 52.6 54.5 Vacuum residue 47.1 45.3 TABLE 1: THE REVAMP INCREASED VGO RECOVERY AND REDUCED VACUUM RESIDUE ENTRAINMENT. 2.2. Coker hydrocracker line-up Delayed coking is often identified as one of the most effective residue upgrading technologies, but there is a misconception in the industry that the resultant HCGO constrains the downstream units. For example, some believe that co-processing HCGO in the hydrocracker precludes it from providing base oil feed. In fact, the latest hydrocracking technology can co-process HCGO and generate a product slate of highquality clean fuels or lubricant base oil feed: the downstream can be completely independent of the upstream (see boxed text: Examples of hydrocrackers with high feed and product slate flexibility, page 10). Consequently, a coker hydrocracker line-up can be an extremely powerful combination. It can result in zero fuel oil production and provide robustness in crude flexibility, which can be very valuable, given the changes in crude diet that are occurring. The coker enables handling of the more difficult residue while the hydrocracker can process the higher nitrogen and more aromatic feed that results from the crude switch. However, refiners considering introducing a coker should always pay special attention to the interfaces with the rest of the plant. As shown in Figure 3, the coker has to integrate with the hydrocracker and with the hydrotreaters, where capacity can sometimes be a constraint. In contrast, adding a different residue upgrading technology, an SDA unit, for example (see Section 2.3), has minimal effect on the rest of the refinery. SRN SR kero HDT 1,2,3 Crude Atmospheric residue SRGO HVU CKN LCGO VGO HCU Naphtha Jet/diesel Vacuum residue DCU HCGO Hydrowax FCCU Lubes Coke FIGURE 3: DELAYED COKING IS A HIGHLY EFFECTIVE RESIDUE UPGRADING TECHNOLOGY, BUT THE INTERFACES WITH THE REST OF THE REFINERY HAVE TO BE CAREFULLY MANAGED. 8

2.3. SDA hydrocracking line-up The combination of SDA and DAO hydrocracking (Figure 4) is one of the lowest capital cost options for residue conversion, especially compared with other direct residue hydrocracking options. Traditionally, DAO had to be processed in a fluidized catalytic cracking unit (FCCU) because of its high metals and CCR content. VGO has about 1 2 ppm metals and 0.5 1.0 wt% CCR, whereas DAO typically contains 15 30 ppm metals and 6 10 wt% CCR. However, these are no longer problematic, as a modern welldesigned catalyst system with demetallization followed by pretreat and cracking catalysts can easily handle this. DAO is a relatively clean hydrocracker feed, with extremely low levels of C7-asphaltenes compared with VGO. Commercial comparative data have shown DAO with C7-asphaltenes as low as 10 wppm whereas the VGO has 700 wppm. Crude Atmospheric residue HVU VGO HCU Naphtha Jet/diesel Vacuum residue Hydrowax FCCU SDA DAO Lubes Asphaltenes HSFO, bitumen, power FIGURE 4: AN SDA HYDROCRACKING LINE-UP PROVIDES LOW-COST RESIDUE CONVERSION. The key is to understand the application of the catalysts specific to DAO. When compared with metals removal from atmospheric residue, metals removal from DAO is a very fast and easy; the trick is to design the reactor conditions so that they slow down the metals removal in order to maximize the metals uptake on the catalyst. The catalyst selection is also important, for both pretreatment and cracking, as it is necessary to strike a balance between selectivity and activity to match the properties of the DAO, including accommodating the very large hydrocarbon molecules in DAO. In practice, DAO can be produced at high yields with minimal detrimental contaminants to the downstream units with an advanced SDA unit. The contaminants that are most unfavorable to the performance of the hydrocracker can show the sharpest partitioning (Figure 5) (see the Grupa LOTOS case study in Section 3.2). Component in DAO, % 100 80 60 40 20 Sulfur Nitrogen CCR Metals Asphaltenes 0 0 10 20 30 40 50 60 70 80 90 100 DAO yield, vol% FIGURE 5: AN ADVANCED SDA UNIT CAN PROVIDE HIGH-QUALITY DAO THAT IS SUITABLE FOR HYDROCRACKING. 9

2.4. Hydrocracking base oils line-up Base oil production is rapidly moving away from solvent-based plants toward the catalytic hydroprocessing route. The base oil quality is much higher and there is less dependence on specific crude source. Moreover, base oil yields are higher and it is easier to make the high-quality Group III base oils demanded by the current market. The combination of hydrocracking plus catalytic base oil plants is aligned with the refining strategy for processing more difficult crudes, with the hydrocracker being the key enabling unit. Figure 6 shows a typical line-up. In the high-vacuum unit (HVU), deep-flash technology can be used to maximize feed heaviness. The hydrocracker s conversion can be fine-tuned to balance product qualities and yields, and the catalytic dewaxing/hydrofinishing (CDW/HF) unit can generate the base oils for group II or III products, as appropriate. If there is sufficient demand for heavier (500N) base oils, DAO can also be added (see the Hyundai Oilbank case study in Section 3.1). The processing route using C3 DAO will also enable the production of Group II bright stock, a product that currently does not exist in the market but will be in demand as more Group I plants close and the traditional supply of bright stock disappears. Atmospheric residue HVU HVGO HCU CDW/HF Fuel gas Diesel/60N 100N 150N 500N DCU Optional FIGURE 6: THE TYPICAL HYDROCRACKING BASE OILS LINE-UP. EXAMPLES OF HYDROCRACKERS WITH HIGH FEED AND PRODUCT SLATE FLEXIBILITY A brief review of selected units around the world demonstrates that the hydrocracker can successfully process a wide variety of feeds. REFINERY FEEDS KEY PRODUCTS Marathon Garyville, USA Heavy VGO, HCGO, DAO, light cycle oil Middle distillates Valero St Charles, USA VGO, HCGO Middle distillates CNOOC Guangzhou, China VGO, HCGO Middle distillates, base oils, ethylene cracker Grupa LOTOS Gdańsk, Poland VGO, DAO, HCGO* Middle distillates Hyundai Oilbank Daesan, South Korea VGO, HCGO Base oils *HCGO will come with the delayed coker that Grupa LOTOS is currently installing. 10

3. CASE STUDIES 3.1. Hyundai s HVU hydrocracker base oils value chain Hyundai Oilbank identified a strategic opportunity to build a 20,000-bbl/d Group II lubricant base oil manufacturing plant adjacent to its Daesan refinery in South Korea because demand for Group II products was robust in the region. Hydrocracker bottoms (hydrowax) would provide the feed for the new facility. The new plant would be close to key lubricants markets. It would export a significant proportion of the products to China, the largest consuming market, and other countries in Asia through Shell s global distribution network. Adding the new plant would require several changes to the existing refinery. Analyses revealed that, to get the right amount of feed at the right quality, the hydrocracker needed revamping to: increase throughput from 35,000 to 40,000 bbl/d; decrease conversion from 68 to 50% and target hydrowax with a viscosity index of 125; and increase the cycle length from three to four years to align with the new base oil plant. To achieve this, several relatively inexpensive changes were made. In the reactor section, for example, new reactor internals and catalysts were installed, and a new high-pressure effluent exchanger was added. In the fractionator, the hydrowax rundown hydraulic system was upgraded. In addition, the unit s conversion was reduced to increase the amount of hydrowax. To get sufficient and suitable feed for the hydrocracker, it was also necessary to go further back into the processing stream and revamp the HVU. The HVU revamp involved: replacing key internals with new packing, draw trays and a spray distributor; modifying the convection sections of both furnaces; upgrading the vapor-horn-type feed inlet device to the latest-generation technology; and upsizing the transfer line and the column feed inlet nozzle. Figure 7 shows how the project changed the refinery configuration. It increased the unit s capacity and enhanced the potential for making heavy base oils as opposed to light ones. A hydrocracker on a diet of conventional VGO typically makes very light base oils, mostly in the 2 6-cSt range and some in the 6 8-cSt range. In contrast, Hyundai is producing a substantial amount of base oil in the 10 12-cSt range. This is only possible because its HVU can lift very heavy VGO and closely control the levels of asphaltenes, CCR and metals. As a result, the VGO yield increased and its quality specifications were met. The improvement in quality parameters is shown in Table 2. VGO QUALITY PARAMETER PRE-REVAMP POST-REVAMP D1160 T95%, C 540 562 Nickel + vanadium, wppm 0.3 0.5 CCR, wt% 0.4 0.5 TABLE 2: HOW THE VGO PRODUCT QUALITIES WERE CHANGED BY THE REVAMP. 11

CDU-1 AR 56 kbbl/d 20 kbbl/d AR VDU 76 kbbl/d VGO 35 kbbl/d VR DCU HCGO 5 kbbl/d HCU 40 kbbl/d Hydrowax Base oil 20 kbbl/d CDU-2 AR to RDS/RFCC Existing Revamp New FIGURE 7: HYUNDAI S HVU AND HYDROCRACKER WERE REVAMPED AND CONFIGURED TO WORK WITH THE NEW BASE OIL PLANT AS A VALUE CHAIN. Through these changes, the HVU is delivering the VGO feed to the hydrocracker at the right yield and heaviness: the profile is exactly as per design. The hydrocracker is operating at target conversion to deliver the hydrowax quantity and quality that the base oil plant needs. In addition, all this is helping the base oil plant to deliver the right product quality. Construction was completed in a record 20 months (close to two months ahead of schedule) and the base oil complex delivered the first on-specification products in 2014. THE REVAMP IMPERATIVE It is difficult to overstate the importance of the HVU and hydrocracker revamps to Hyundai s overall base oils project. To make the world-scale base oils project fly, Hyundai needed to provide more feed, but the project would have become uneconomical if that had required the installation of new process units. However, it is usually substantially more challenging to revamp a unit than to install a new one. Nevertheless, the refiner, working closely with Shell Global Solutions and Criterion, found ways to costeffectively extract the additional feedstock that was required from the upstream units. Both revamps achieved their objectives and the new base oil plant met its performance guarantees. 12

3.2. Grupa LOTOS unlocks the potential of DAO hydrocracking The Polish refiner Grupa LOTOS was the first refiner worldwide to make operational a new generation of DAO hydrocracking technology. In 2011, it installed the technology as part of a major residue upgrading project called the 10+ Programme. This helped to raise the refining capacity by 75%, focus production on higher-margin diesel fuels, increase market share and enhance margins by $5 per barrel. In addition, the project also helped to dispel the misconception that hydrocracking of DAO means low reliability. As shown in Figure 8, two key process units for the new residue upgrading complex were the: 45,000-barrels-a-day DAO hydrocracker. This processes VGO and DAO and yields finished products, mostly jet fuel and diesel, straight off the unit. It also produces hydrowax, which Grupa LOTOS has found a profitable outlet for as a supplemental feed to its base oil plant. Figure 9 shows the DAO hydrocracker s configuration. advanced SDA unit. This takes in vacuum residue and produces DAO that is sent directly to the hydrocracker. Crucially, this DAO is of a superior quality suitable for hydrocracking because it has lower levels of contaminants such as sulfur, nitrogen, metals and asphaltenes. Naphtha HMU Hydrogen Atmospheric residue HVU VGO HCU Jet Diesel DAO HCGO Vacuum residue SDA DCU Coke FIGURE 8: GRUPA LOTOS S DAO HYDROCRACKER RUNS ON A FEED OF 50% VGO AND 50% DAO, AND PRODUCES A HIGH-QUALITY PRODUCT SLATE THAT INCLUDES ULTRA-LOW-SULFUR DIESEL. A DELAYED COKER, WHICH GRUPA LOTOS IS ADDING AS A SUBSEQUENT PROJECT, IS ALSO SHOWN. 13

Fresh feed H 2 H 2 H 2 Gas/LPG LN HDM HDS HC HN Jet HDN Diesel R-01 demetallization R-02 demetallization R-03 cracking Hydrowax FIGURE 9: GRUPA LOTOS DAO HYDROCRACKER FEATURES A DEDICATED HDM REACTOR, FOLLOWED BY HYDROTREATING AND HYDROCRACKING REACTORS. For the first three months, the hydrocracker processed VGO from Urals crude: a traditional high-nitrogen feed. Next, 50% DAO was added (the feed qualities are shown in Table 3) and Grupa LOTOS worked with Shell Global Solutions and Criterion to optimize the hydrocracker s performance. In incremental steps and with careful monitoring, the net conversion increased from the original design level of 60% in once-through mode to 85% conversion in recycle mode. In subsequent years, the DAO feed quality became progressively more difficult (Table 4). Even at this duty, the unit has shown excellent reliability and has achieved a four-year cycle with very stable temperatures (Figures 10 11). VGO DAO Specific gravity 0.925 0.9497 Sulfur, wt% 1.9 2.3 Nitrogen, ppmw 1,573 2,664 Total Ni + V, ppmw <1/<1 6/11 CCR, wt% 0.8 3.8 >540 C, wt% 3 75 T95%, C 535 698 TABLE 3: THE UNIT S FEED QUALITIES IN 2011. VISCOSITY AT 100 C, CST CCR, WT% NICKEL, PPMW VANADIUM, PPMW NITROGEN, PPMW >550 C, WT% 2011 70.9 4.6 5.3 12.0 3,004 70.1 2012 74.8 4.8 5.8 13.3 3,305 71.0 2013 91.6 5.2 5.4 14.0 3,125 79.2 2014 94.2 5.3 5.7 14.6 3,397 76.4 2015 85.1 5.2 4.5 10.6 2,586 70.6 2016 90.6 5.4 5.4 13.7 2,575 77.9 TABLE 4: THE AVERAGE DAO FEED QUALITY IN SUBSEQUENT YEARS OF OPERATION. 14

100 Plant conversion (%woff) Weight on feed, % 90 80 70 60 0 200 400 600 800 1,000 1,200 1,400 1,600 1,800 2,000 2,200 Days onstream FIGURE 10: THE DAO HYDROCRACKER, WHICH IS CURRENTLY RUNNING AT ABOUT 85% CONVERSION AND PROCESSING AN EXTREMELY DIFFICULT FEEDSTOCK, HAS ACHIEVED MORE THAN 1,900 DAYS ON STREAM. +40 Pretreat catalyst average bed temperature Temperature, C +30 +20 +10 Base 0 200 400 600 800 1,000 1,2001,400 1,6001,800 2,0002,200 Bed 1 average temperature Bed 2 average temperature Days onstream Bed 3 average temperature Bed 4 average temperature +70 HC actual WABT and apparent deactivation rate Temperature, C +56 +42 +28 +14 Base 0 200 400 600 800 1,000 1,2001,400 1,6001,800 2,000 2,200 Days onstream Actual cracking WABT, C FIGURE 11: THE TEMPERATURES IN THE PRETREAT (TOP) AND CRACKING CATALYST BEDS (BOTTOM) HAVE BEEN EXTREMELY STABLE, WHICH DEMONSTRATES THE HIGH PERFORMANCE OF THE CATALYST SYSTEM. Another key metric in DAO hydrocracking is the performance of the demetallization catalyst system, as this determines the unit s ability to achieve a feed quality for the pretreat catalyst that is more consistent with that of a very heavy VGO feed. The demetallization catalysts installed at Grupa LOTOS are specialty demetallization catalysts that have a very high activity for metals removal, a high metal uptake capacity and a high crush strength. 15

100 99 HDM, % 98 97 96 Metals on catalyst, % 95 94 0 200 400 600 800 1,000 1,200 1,400 1,600 1,800 2,000 2,200 Days onstream HDM Metals on catayst FIGURE 12: THE DAO HYDROCRACKER HAS SHOWN SUSTAINED DEMETALLIZATION PERFORMANCE. As shown in Figure 12, the deactivation rate of the demetallization catalyst has been low and is on target for the planned cycle length and turnaround date. Metals uptake (red series) has been steady and the demetallization removal efficiency (blue series) has been near 100% (99.4%) over the cycle. Like Hyundai, Grupa LOTOS is also unwilling to stand still. It is currently installing a delayed coker as part of its EFRA (effective refining) project that will enable HCGO to be added to the unit s diet. GRUPA LOTOS S HIGHLY FLEXIBLE ASSET Since its DAO hydrocracker came on stream in 2011, Grupa LOTOS has worked with Shell Global Solutions and Criterion to adapt the operation of this unit as its situation and objectives have changed. The unit s extreme feedstock flexibility has been key: its feed diets have already varied from 100 to 50% VGO with 50% DAO. It also processes furfural extracts, which contain high levels of heavy aromatics, and, when the delayed coker comes online in 2018, it will co-process another difficult feed, HCGO. In addition, it has operated in both once-through and recycle modes, and operated at conversion levels between 60 and 90%. 16

4. KEY TAKEAWAYS Now is one of the most challenging periods that the industry has ever known, but many refiners worldwide have maintained or enhanced their competitiveness by leveraging the flexibility of their hydrocrackers. For example, some are processing heavier, cheaper crudes and non-standard feeds such as HCGO and DAO. In so doing, they can capture substantial bottom-line benefits, providing they can mitigate the challenges of these highly challenging feeds. Likewise, although middle distillates often provide a higher-value product stream, the economics in some regions are better for lubricant base oils or petrochemicals, and many refiners have been able to exploit them. However, this change requires a significant modification to operating strategies, as the conversion level is dialed down and the quality of the unconverted residue becomes key. REFERENCE LIST Customers that have licensed Shell Global Solutions hydrocracking technology, or that have worked with us to revamp their unit, include: Hyundai Oilbank, which worked with Shell Global Solutions to revamp the hydrocracker at its Daesan facility in South Korea to reduce conversion so that the bottoms product could feed a new Group II lubricant base oils plant (for more on this, see section 3.1); Grupa LOTOS, Poland s second largest refiner, which started up a new-generation 45,000-bbl/d DAO hydrocracker at its Gdańsk refinery and then, in its first cycle, increased the conversion rate from 60 to 85% to produce more jet fuel and Euro 5 diesel (for more on this, see section 3.2); Valero, North America s largest refiner, which licensed a 50,000-bbl/d, unified-design, two-stage hydrocracker at each of its refineries in St Charles, Louisiana, and Port Arthur, Texas, USA; CNOOC, which selected Shell Global Solutions dual-service hydrocracking process for its refinery in Guangzhou Province, China. At 80,000 bbl/d, this is the highest capacity hydrocracker operating in the country. It has the flexibility to operate in integration mode with the ethylene cracker at Nanhai Petrochemicals Complex and the refinery s FCC unit. Marathon Oil Corporation, which recently revamped its Shell-licensed hydrocracker at its Garyville refinery in Louisiana, USA, to increase its capacity from 77,000 to 115,000 bbl/d; Shell Deer Park Refining Ltd s Deer Park refinery, USA, which commissioned Shell Global Solutions to reconfigure its hydrocracker from full conversion to partial conversion in order for it to produce ethylene cracker feed; Preem AB, Sweden s largest refiner, which worked with Shell Global Solutions to revamp the 53,000-bbl/d hydrocracker at its Preemraff Lysekil facility to overcome operational issues and increase middle distillates capacity; and North Atlantic Refining Company, which adopted Shell Global Solutions reactor internals and Criterion catalysts when it originally revamped the single-stage, 37,000-bbl/d hydrocracker at its refinery in Newfoundland, Canada. 17

THE AUTHOR John Baric, Licensing Technology Manager, Shell Global Solutions, has worked in the refining/chemicals industry for 35 years. He has fulfilled roles in operations, technical services, business development and capital projects over a period that has seen substantial changes in environmental legislation, especially clean fuels, the emergence of oil sands upgrading technology, and unprecedented development of catalysts and process technologies. ABOUT SHELL GLOBAL SOLUTIONS Shell Global Solutions provides technical consultancy and licensed technologies for the Shell Group and third-party customers within the energy industry. Shell Global Solutions strives to deliver innovative technical solutions and effective technology to support its customers in their day-to-day operations and delivery of strategic plans to improve the capacity and performance of existing units; integrate new process units into existing refineries and petrochemical complexes; incorporate advanced proprietary catalyst systems (CRI/Criterion) and reactor internals; through to the design of grassroots refineries. Shell Global Solutions is affiliated with Shell s catalyst companies, which innovate and sell catalysts through a network that includes Criterion, Zeolyst International, CRI Catalyst Company and CRI Leuna (formerly known as Kataleuna). Shell is one of the largest hydrocracker operators in the world, with a capacity of more than 500,000 bbl/d. Shell Global Solutions provides technical support to over 50 sites worldwide. It has signed 12 hydrocracking licenses in the last five years, and has more than 60% of the hydroprocessing reactor internals market. Criterion Catalysts & Technologies (Criterion) is a global leader in hydroprocessing catalysts and has a track record of over 50 years. For further information, please visit our website at www.shell.com/globalsolutions 18

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