New technologies to meet the low sulfur fuel challenge.

G. F. Stuntz, ExxonMobil Research & Engineering, U.S.A.; F. L. Plantenga, Akzo Nobel Catalysts BV, The Netherlands Abstract
Regulations to reduce the sulfur level in gasoline and automotive diesel to less than 50 ppm are in place or planned in many countries. A number of technologies have been developed to enable production of these fuels. For instance, SCANfiningTM I is a highly selective process for reducing sulfur in fluid catalytic cracked (FCC) naphtha with minimum olefin saturation/octane loss. Recently ExxonMobil announced the development of SCANfining II, a process that can selectively reduce even the sourest FCC naphthas to ppm sulfur levels with low octane loss. Both of these processes use RT-225, a catalyst jointly developed and commercialized by ExxonMobil and Akzo Nobel. These companies have also recently completed the development of NEBULA, a hydroprocessing catalyst with more than double the activity of any other commercial catalyst at medium-high pressures. NEBULA has recently been applied in several refinery distillate hydrotreaters and is performing as expected. Some countries are now considering reducing fuel sulfur even lower, to 10-15 ppm or less. Achieving this ultra-low sulfur level without large additional expenditures is a major challenge. Both ExxonMobil and Akzo Nobel are continuing to develop new catalyst and process technology options to help the refining industry meet these future needs.

Introduction
Advanced designs of transportation vehicles to reduce air pollution have become increasingly dependent on the availability of low sulfur (S) fuels. Substantial reductions in gasoline and diesel sulfur levels have already begun to occur in some parts of North America, Europe, and Japan. This trend is expected to accelerate as additional regulations mandating 10-50 ppm S become effective between 2004-2008 in the U.S., Canada, Europe and elsewhere around the globe. Meeting the new low sulfur fuel specifications presents a significant challenge to the petroleum refiner. In order to minimize the cost of producing these fuels, new technology advances are needed. For gasoline, the greatest challenge is to deeply desulfurize fluid catalytic cracked (FCC) naphtha (which contributes most of the sulfur in gasoline), while minimizing the loss of octane resulting from olefin hydrogenation during the desulfurization step. For diesel, the objective is to achieve the ultra-low sulfur specifications at the lowest possible cost. The application of improved catalyst technologies, along with effective molecule management in the refinery offer the greatest potential for achieving this objective. ExxonMobil and Akzo Nobel are committed to developing cost-effective process and catalyst technology options for meeting current and future needs for mogas and diesel sulfur removal. ExxonMobil has commercialized the SCANfining process for producing ultra-low sulfur gasoline with minimum loss of octane1,2. The RT-225 catalyst utilized in SCANfining was jointly developed by ExxonMobil and Akzo Nobel. New diesel hydroprocessing catalyst technologies, including Akzo Nobel's STARS family of catalysts and a breakthrough catalyst called NEBULA, which was also jointly developed by ExxonMobil and Akzo Nobel, have also been developed and commercialized. The most effective utilization of these advanced technologies is enabled by having a detailed understanding of the molecular composition of the gasoline and diesel streams and managing the sulfur components so that they can be removed at the lowest possible cost.

Chemistry of Sulfur Removal in Gasoline

Since most of the sulfur present in today's gasoline is derived from the naphtha produced from the fluid catalytic cracker, one option for reducing gasoline sulfur is to hydrotreat the feed to the FCC unit. Although this option can help remove much of the sulfur and provides improved yields from the FCC unit, it requires a very significant capital investment and usually is not able to remove enough sulfur to reach ultra-low sulfur targets. Thus, desulfurization of the FCC naphtha is most often the preferred approach. Figure 1 highlights the primary reactions associated with sulfur removal from FCC naphtha.

Mercaptans

R-SH R-SH

Caustic Treat Hydrotreat

R-S-S-R R-H + H2S R-H + H2S

Thiophenes

Hydrotreat

R=R Additional Reactions R = R + H2S

Hydrotreat

R-R

Recombination

R-SH

Figure 1. Chemistry of Sulfur Removal From FCC Naphtha FCC naphtha contains significant amounts of low boiling mercaptan sulfur species. These can be readily removed either by caustic treatment to convert them to disulfides which are extracted or they can be converted directly by hydrotreating. FCC naphtha also contains higher boiling thiophenic sulfur species. These sulfur species are more difficult to remove and generally require hydrotreating. An undesirable side reaction of hydrotreating is the hydrogenation (or saturation) of olefins which results in a loss of octane decreasing the value of the low sulfur gasoline. Another undesirable side reaction which can occur is the reaction of olefins with H2S which results in the formation of higher boiling mercaptans. A detailed knowledge and understanding of the types and amounts of sulfur and olefin molecular species present is crucial to selecting the optimum desulfurization technology options(s) for meeting ultra-low sulfur targets. ExxonMobil has developed predictive tools and models allowing accurate projections to be made for the amount of sulfur in FCC naphtha and how the different types of sulfur molecules behave in various desulfurization technology options.

SCANfining Process And Catalyst

ExxonMobil and Akzo Nobel recognized the need for a catalyst that would permit selective hydrodesulfurization (HDS) of FCC naphtha while minimizing the saturation of olefins. The patented, selective HDS catalyst, RT-225, resulting from a joint development and commercialization between ExxonMobil and Akzo Nobel was first proven in 1995 in the original SCANfining unit in ExxonMobil's Baton Rouge, LA refinery. Multiple commercial batches have been produced and the RT-225 catalyst has now been proven in several additional SCANfining units in Europe and Asia. The successful commercial experience of RT-225 has proven that three to four year catalyst life cycles are now possible. The SCANfining process combines the outstanding selectivity of RT-225 with optimized process conditions that favor HDS reactions over olefin saturation. This provides maximum octane retention and minimizes hydrogen consumption. The SCANfining process is based on a simple, conventional fixed bed reactor design with relatively low operating pressure and temperature and a very simple flow plan. Thus, the capital investment for SCANfining is significantly less than for other more complex desulfurization technology options. Furthermore, the RT-225 catalyst and SCANfining process can often be retro-fitted into existing reactors providing sizable capital investment savings.

SCANfining Offers Multiple Configuration Options

Light cat naphtha, or LCN, nominally the C5-C6 hydrocarbon fraction, generally contains more than half of the olefins in the full range naphtha, but less than 10% of the sulfur. In the past, blending of LCN into gasoline and desulfurizing only the heavier, less olefinic fractions has been a viable approach to meet

gasoline sulfur targets. However, with gasoline sulfur specifications moving to the 10-50 ppm range, refiners will need to address LCN sulfur removal as well. The majority of the sulfur species in LCN are thiols- primarily ethyl, i-propyl, and n-propyl mercaptan. Thiophene, the lowest-boiling non-mercaptan sulfur compound present in substantial quantity, has a pure compound boiling point just above the C6 range, at 357K. However, in real mixtures, non-idealities in the system, combined with practical limits on fractionator efficiency, limit how deep the LCN fraction can be cut without significant "bleed" of thiophene into the lighter fraction. ExxonMobil has developed predictive tools for optimizing the design of such fractionators.1,2 Detailed knowledge of the molecular nature of LCN sulfur species is required to select the optimum process for desulfurizing LCN. Figure 2 illustrates three different approaches ready for commercial application which each address desulfurization of the LCN stream3. Option 1 is to separate the LCN via fractionation and desulfurize it using conventional caustic extraction facilities. This option can be especially attractive if fractionation equipment and/or mercaptan extraction facilities are already available in the refinery. As discussed above, a detailed knowledge of the sulfur species present is required to define the LCN cut point in the fractionator where the ultra-low sulfur target can still be met.

Option 1 Fractionate/ extract

Caustic extraction

Full range Cat naphtha

Option 2 Pretreat, fractionate

Pre-treat Step, Sweeten Plus

G A S O L I N E P O O L

Option 3 Wide-cut SCANfining

SCANfiner

Figure 2. LCN Desulfurization Options A second option (Option 2) is to pre-treat the FCC naphtha to increase the boiling point of the light mercaptan sulfur species. ExxonMobil's Sweeten Plus process converts the mercaptans to disulfides using a conventional caustic sweetener. The disulfides are then separated by fractionation and desulfurized with the thiophenic sulfur species in the fractionator bottoms. The resulting LCN is low enough in sulfur to be blended directly into the gasoline pool. The simplest option (Option 3) is direct processing of the LCN in a wide-cut SCANfiner. This option has the obvious benefit that it does not require a fractionator, and does not require separate LCN processing equipment. On the surface, it might appear that a significant disadvantage of this approach is that the highly olefinic LCN fraction is exposed to SCANfining conditions and catalyst, resulting in some hydrogenation of olefins and octane loss. In fact, the loss of octane is in many cases quite modest. The reason for this is that octane loss for branched C5 and C6 olefins upon hydrogenation is relatively small compared to C7-C8 olefins. In one instance, the saturation of 2-methyl-2-butene (the most common C5 olefin in FCC naphtha) actually results in a small increase in motor octane number (MON)3. Thus, SCANfining of full range FCC naphthas can result in very small incremental pool octane losses, relative to cases that include fractionation and separate LCN processing. Table 1 presents data derived from pilot plant studies on full range FCC naphtha and an intermediate cat naphtha (ICN) / heavy cat naphtha (HCN) fraction from the same feed. Both feeds were processed using SCANfining at the same temperature, pressure, and hydrogen treat gas rate. Space velocity was adjusted to give 42 ppm S in the

treated full range naphtha. For the ICN/HCN fraction, product sulfur was adjusted to a level that would give the same 42 ppm S when blended back together with the caustic treated LCN. Research and Motor Octane values for the feeds and the SCANfined products were determined by engine tests. The octane values for the blend of caustic treated LCN and SCANfined ICN/HCN were determined by paper blending, using the measured values for the SCANfiner product, and assuming no loss of octane in caustic extraction of the LCN. Full range FCC naphtha feed 792 91.5 79.7 SCANfined full range FCC naphtha 42 90.3 80.1 SCANfined ICN/HCN + caustic extraction LCN 42 90.7 79.8

Sulfur (ppm) RON MON

Table 1: Comparison of Wide-cut and ICN/HCN SCANfining Within the accuracy of the octane measurement, there is no significant change in MON in the product from either full range naphtha or ICN/HCN SCANfining in this example. RON losses are quite small (0.81.2 RON), with the loss in the full range case being marginally higher than for the separate LCN and ICN/HCN processing. Clearly, with this particular feed and processing objective, investment in a fractionator and separate LCN processing equipment would be difficult to justify, and especially so in a MON-limited gasoline pool.

"No Regrets" Pathways For Meeting Future 10 ppm Sulfur Regulations

While many low sulfur regulations over the next several years are calling for levels of 30-50 ppm in blended gasoline, as noted earlier there are some locations in which a move toward 10 ppm sulfur is underway. When investing in technology to meet the 30-50 ppm specifications, it is prudent to consider what options would be available for migration to an even lower sulfur environment. SCANfining offers a number of options which maximize utilization of investment made for 30-50 ppm ("no regrets" path), while minimizing additional investment required to achieve 10 ppm sulfur later. Not surprisingly, the best option will depend on a range of critical variables, including FCC naphtha sulfur and olefin levels, octane value, and the approach taken to meet the initial 30-50 ppm target. An example based on pilot plant data obtained on a group of relatively low sulfur full range FCC naphtha feeds (500-1200 ppm sulfur) is provided here to illustrate a robust SCANfining technology option for extension to the 10 ppm product sulfur range.
6
Curve A: Low Sulfur, SCANining I

5 Octane Loss (R+M)/2

Curve B: High Sulfur, SCANfining I Curve C: High Sulfur, SCANfining II

2
C

0 0 20 40 60 80 100 Product Sulfur, ppm

Figure 3: Impact of lower sulfur targets

For a refiner with a relatively low sulfur (~500 ppm), moderate olefin content full range FCC naphtha, and no existing FCC naphtha fractionation capability, curve A in Figure 3 shows that wide-cut SCANfining I would result in a 0.1 to 0.3 (R+M)/2 octane loss in the FCC naphtha upon desulfurization to the 30-50 ppm range. With little or no additional investment, the same unit could produce 15 ppm S product with a loss of about 1.3 (R+M)/2. Alternatively, a fractionator could be added, along with one of the LCN processing options already discussed, to further reduce octane loss.

SCANfining - II
The original SCANfining process (SCANfining I) provides a simple option for removing sulfur from most FCC naphtha feeds. However as shown by curve B in Figure 6, for FCC naphthas having very high sulfur content (e.g., ~3000 ppm S), the octane loss can become severe as 10 ppm sulfur in the product is approached using SCANfining I. Upgrading to SCANfining II provides an option to greatly mitigate this octane loss as shown by curve C. Full use of the SCANfining I equipment can be made and the additional capital investment is only 30-40% of the original SCANfining I process.

SCANfining with EXOMER

As an alternative approach to reach ultra-low product sulfur levels with high sulfur feeds, one can use a new technology, called EXOMER. EXOMER was jointly developed by ExxonMobil and Merichem, building on extensive commercial experience in related heavy mercaptan removal service4. EXOMER is designed to remove mercaptans that are formed during SCANfining from recombination of H2S and olefins. These heavy mercaptans cannot be removed by conventional caustic extraction treating. In the example shown in Figure 4, addition of EXOMER to SCANfining I allows the refiner to achieve 10 ppm sulfur product with under 1.0 road octane loss. If sulfur blending flexibility exists, at a product sulfur target of 15 ppm, road octane loss with EXOMER can be reduced to 0.7 to 0.8.
6

5 Octane Loss (R+M)/2

Full Range FCC Naphtha - 1000 ppm S Moderately High Olefin Content

SCANfining I

1
SCANfining I with EXOMER

0 0 20 40 60 80 100 Product Sulfur, ppm

Figure 4. SCANfining with EXOMER

SCANfining Commercial Experience.

Over the last six years, an extensive commercial database has been established, demonstrating the performance of SCANfining I and the RT-225 selective catalyst in multiple units. These units have operated with feed sulfur levels as high as 2300 ppm, and product sulfur levels as low as 25 ppm, and with feeds ranging from full range FCC naphtha to ICN and ICN/HCN blends. SCANfining has been proven in North America (ExxonMobil Baton Rouge Refinery), in Europe (ExxonMobil Port Jerome Refinery), and in Asia (Bazan Oil Refineries, Haifa, Israel and LG-Caltex, Yosu, Korea). As the pace of regulatory change has accelerated, so has the interest in this technology. Including the commercial units above, ExxonMobil and SCANfining licensees have made commitments to build SCANfining units totaling well over 500 kB/D of capacity. With this broad application base, continuing pressure on sulfur levels, and increasing octane values, there will clearly be a strong incentive to provide solid support for

the technology, and to continue to seek further improvements. ExxonMobil's commitment to improving the technology has been demonstrated with the development of SCANfining II, wide-cut SCANfining, options for LCN processing such as Sweeten Plus, EXOMER, and a variety of improved kinetic and predictive tools. In addition, new technology developments are currently underway that should offer even greater octane retention and flexibility towards meeting future 10 ppm sulfur specifications

Chemistry Of Sulfur Removal In Diesel

In contrast to more conventional desulfurization to levels of 350-500 ppm sulfur in diesel, the primary sulfur components that have to be removed when producing 10 ppm sulfur are relatively unreactive dibeta-substituted dibenzothiophenes. The desulfurization reaction mechanism of this type of sulfur species typically proceeds via a hydrogenation step of the aromatic system, as shown in Figure 5. This contrasts with the more typical desulfurization route that proceeds via direct hydrogenolysis5,6,7. This difference in reaction mechanism indeed opens new ways to improve catalyst activity and to find better process conditions to produce ultra-low sulfur diesel.

H3 C

CH3

Hydrogenation Route Direct Route

H3 C

CH3

H3 C

CH3

H3 C

CH3

Figure 5: Reaction mechanisms for sterically hindered dibenzothiophenes While production of 10-50 ppm sulfur diesel can be achieved with the older generations of catalysts, the challenge is to do this in a cost efficient manner using a relatively small reactor and with minimum hydrogen consumption. Since the mid-1990's, many refineries have already made capital investments in installations to produce 350-500 ppm sulfur diesel. It would therefore be very attractive if these refineries would not need to invest again in new equipment to produce 10-15 ppm sulfur. Figure 6 shows the increase in reactor volume, as indicated by liquid hourly space velocity (LHSV) that would be needed using conventional catalysts to meet the new sulfur specifications. Holding other parameters constant, reducing the required sulfur from 500 ppm down to <10 ppm can result in as much as a four fold or greater increase in reactor volume being required. The challenge in diesel desulfurization technology, then, is to minimize the need to invest in additional reactor volume or additional hydrogen pressure, both of which can result in significant capital costs.

4 3 2 1 0

cat

500

1000 Product Sulfur, ppm

1500

2000

Figure 6: Impact product S on required reactor volume One way to avoid or reduce the need for increased reactor volume is to develop more active desulfurization catalysts. Through a combination of advanced catalyst technology and process conditions selected based on a detailed knowledge of the molecular sulfur species in diesel, ultra-low sulfur diesel targets can often be achieved using existing facilities.

Diesel Desulfurization Catalyst Advances

In the past, continual catalyst technology improvements have been important contributors to the refiners ability to meet new sulfur specifications. Over the past few years, however, desulfurization catalyst technology has experienced a step change advance in performance. Akzo Nobel/Nippon Ketjen have introduced the STARS and NEBULA catalyst families to produce diesel fuels with a sulfur content of less than 10-15 ppm.

STARS Catalyst Technology

The STARS technology concept produces a new generation of catalysts with Super Type II Active Reaction Sites, with superior activities5,8. In comparison to the type I active sites present on conventional catalyst, these type II active sites have a very high intrinsic activity for hydrodesulfurization (HDS), hydrodenitrogenation (HDN), and hydrodearomatization (HDA) reactions. The new technology is applicable to both NiMo and CoMo catalysts, called KF-848 and KF-757, respectively. KF-757 has up to 60% more activity than its predecessor, KF-756, especially designed for units operating in the ultra-deep HDS mode. Figure 7 shows the progression of catalyst performance over the years. Catalyst companies such as Akzo Nobel/Nippon Ketjen have succeeded in continually introducing more active catalysts in response to the introduction of new specifications, which has helped refiners achieve progressively lower diesel sulfur levels at significantly reduced cost. The STARS technology represented a shift in the technology "s-curve" and, as a result, has exhibited rapid penetration into the diesel desulfurization market.

450 400 Relative Volumetric Activity 350 300 250 200 150 100 50 1500 ppm 500 ppm 350 ppm

STARS

CoMo Alumina

0 1950 1955 1960 1965 1970 1975 1980 1985 1990 1995 2000 2005 Year

Figure 7: Historical progression of HDS catalyst activity Currently, the most widely employed catalyst system is the KF-757, the CoMo version of the STARS family, which is particularly responsive under low pressure operations. Since its introduction, it has been loaded into more than 100 units worldwide. In Germany, the leading market for ultra-low sulfur diesel, KF-757 has a market share of over 80%! KF-848, which is particularly suited for moderate or high pressure units, is currently in use in 5 diesel units in Europe, some of which are currently producing <10 ppm sulfur diesel on a regular basis.

NEBULA
Akzo Nobel and ExxonMobil recently completed the development of the NEBULA catalyst as an option for helping to meet ultra-low sulfur diesel requirements for certain applications9,10. Figure 8 compares NEBULA to KF-848 in terms of reactor temperature required to reach ultra-low sulfur levels. NEBULA offers a phenomenal activity advantage of 20 K at 10 ppm S. Thus, this breakthrough catalyst system offers a factor of two advantage in catalyst activity under moderate pressure applications. In addition, NEBULA provides similar activity advantages for HDN and HDA
645 640 635 630 625 620 615 610 605 0 5 10 15 Product Sulfur, ppm 20 25 30 NEBULA KF 848 Avg. Reactor Temp., K

20 K Activity Advantage

Figure 8. NEBULA breakthrough activity

NEBULA was introduced into the market in mid-2001 and is currently in use in three units and all applications are confirming the step change in activity versus historical catalysts. At this point in time the NEBULA-1 catalyst is significantly more expensive than conventional desulfurization catalysts and therefore its application is only economically attractive if the extra added value for the refinery is much larger than the additional costs, such as when investment in additional hydroprocessing facilities are required. An example of this situation is the second commercial application of NEBULA-1, where the catalyst application enabled the refiner to produce <10 ppm sulfur diesel at full throughput without a unit revamp in a unit that was previously producing 350 ppm S diesel with KF-757 STARS11.

Molecule Management
While improvements in HDS catalyst technology have been key in meeting new low sulfur diesel targets, effective management of the molecules coming into the refinery is also critical to meeting future mogas and diesel fuel specifications. As discussed above, defining the optimum strategy for FCC naphtha desulfurization technology requires a detailed knowledge of the distribution and amounts of sulfur and olefinic molecules in the FCC naphtha. For achieving ultra-low sulfur diesel, the key to the design of a low cost, efficient process also lies in a thorough understanding of both the catalyst and process. The detailed characterization and kinetics of sulfur-containing species has been an active area of interest since diesel sulfur species have widely differing reactivities. Since hundreds of distinct sulfur-containing molecular species can be effectively separated and identified with a capillary GC and sulfur specific detector, some "lumping" is required to simplify the task of modeling how these sulfur species will behave during desulfurization. The relative rates of reaction of different sulfur "lumps" have been found to differ as much as ten fold. The sulfur-containing molecular classes also differ by boiling point and include non-aromatic non-thiophenes (e.g., sulfides, disulfides, mercaptans), aromatic thiophenes, and three-ring aromatic dibenzothiophenes (DBT's). Depending on the location of alkyl substituents, DBT's can vary greatly in reactivity. For example, DBT or DBT with substitutions in non-beta positions relative to the sulfur atom is relatively reactive. A methyl or ethyl substituent in the beta position relative to the sulfur atom sterically hinders reactivity and is moderately reactive. DBT's with alkyl substitution in both beta positions results in a very difficult molecule to desulfurize. A separate category, unassigned 3 and 4-aromatic ring sulfur types, includes molecules which are difficult to identify due to their complexity and typically low concentrations. These are classified as moderate to difficult in reactivity. In addition, an unassigned 1 and 2-ring-aromatic sulfur category was applied to a class of poorly resolved compounds which elutes over a wide range of retention times. This category is also moderately reactive.

25,000

R
20,000

Sulfur, ppm

R Very Rapid HDS

Di-beta-Dibenzothiophenes Unassigned 3,4 arom ring S B Dibenzothiophenes Unassigned 1,2 arom ring S Non-beta-Dibenzothiophenes Non-thiophenic S Benzothiophenes

15,000

Moderate HDS

10,000

5,000

H
0 438-552 572-583 594-600 605-611 616-627 639+

R
Boiling Range, K

Rapid HDS

Slow HDS

Figure 9. Distribution of sulfur species in diesel

It has also been recognized that the various sulfur types are not evenly distributed across the boiling range of distillate feeds. This effect is illustrated in work carried out by ExxonMobil on a straight-run distillate derived from Arab Medium Crude12. The feed was fractionated into 11 cuts and the sulfur lumps determined as shown in Figure 9. The lighter cuts contain easy to moderately reactive sulfur types (e.g., benzothiophenes, non-beta substituted DBT's) that undergo rapid HDS. The heavier cuts contain the most difficult sulfur types such as di-beta-substituted DBT's. Difficulty converting these species is a key reason HDS unit performance suffers as the distillation endpoint rises. ExxonMobil has assembled an extensive database on cracked and virgin feeds over hundreds of combinations of operating conditions and feedstocks. These data were used to regress rate constants, activation energies, hydrogen partial pressure constants, etc. for the various sulfur types providing a model that has proven to be highly effective in designing and predicting the performance of existing reactor systems. Through a combination of using high activity catalysts, optimizing process conditions, and careful control of sulfur types present via distillation endpoint control, it is often possible to meet ultra-low sulfur diesel targets using existing facilities. ExxonMobil continues to improve analytical techniques allowing molecular speciation of crude oil and modeling tools allowing prediction of how each molecule is transformed throughout the refining process13,14. This knowhow is proving invaluable in the identification of the most cost effective options for removing sulfur from gasoline and diesel.

Conclusions
Environmental regulations requiring 10-50 ppm sulfur in gasoline and diesel will take effect soon in many countries. SCANfining is a proven commercial process which can help meet these targets for gasoline in a cost effective manner, by selectively removing sulfur from FCC naphtha with minimum octane loss. SCANfining can be applied to full range naphtha, with surprisingly small octane losses in many cases. Alternatively, several technologies are available which involve fractionation and separate processing of LCN; these technologies can readily be coupled with SCANfining of ICN or ICN/HCN to further reduce octane losses. Retrofitting of spare semi-regen naphtha reformers can be an attractive low-investment option for full-range or split FCC naphthas. A variety of staged investment pathways can be defined, in which refiners can proceed from a 30-50 ppm sulfur environment to a lower sulfur level, without stranding capital, by using variants on SCANfining. These options include moving from SCANfining I to SCANfining II, and addition of EXOMER to SCANfining. Growing commercial experience is demonstrating that run lengths in excess of three years can be expected with SCANfining. Finally, with a number of units commercialized, and numerous others either under construction or in design, SCANfining is rapidly becoming a well-established technology, with a very positive outlook for future support and improvement. The drive for lower sulfur diesel has triggered an acceleration in catalyst development over the last few years. Akzo Nobel Catalysts and Nippon Ketjen have introduced two new technologies, STARS and NEBULA (with ExxonMobil), that have greatly helped the refining industry to reach the new targets. STARS has become the workhorse technology for the production of ultra-low sulfur diesel and NEBULA has proven to offer breakthrough activity and to be a drop-in solution in some cases allowing refiners to avoid costly investments in new reactors. The development of new and improved technology will not stop here, but it will continue as future market and regulatory demands will also continue to change.

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