Fuels For The 21st Century

Fuel Sulfur Solutions Hydrogen Solutions MTBE Solutions Benzene Solutions

Changing regulations about fuel sulfur have refiners concerned about what might be needed to meet them. Here are some ideas:
Refinerywide Implications of Producing Low-Sulfur Fuels Exploiting Synergy between FCC and Feed Hydroprocessing to Improve Refinery Margins and Produce Low-Sulfur Fuels The Lower It Goes, the Tougher It Gets Meeting Gasoline Pool Sulfur and Octane Targets with the ISAL Process More on the ISAL process FCC Light Cycle Oil: Liability or Opportunity?

Fuel Sulfur Solutions

Within the next few years, European and U.S. governmental regulations will require refiners to drastically lower the sulfur content of gasoline as part of the continuing effort to reduce air pollution from gasoline and diesel engines. Sulfur is targeted because it significantly reduces the efficiency of vehi cle catalytic converters. Emissions of SO 2 and other contami nants from the fluid catalytic cracking (FCC) regenerator and from refinery heater stacks continue to be an issue with refin ers throughout the United States and the rest of the world. For most refiners, the major source of sulfur in gasoline and diesel fuels comes from components produced by the FCC unit. Regenerator stack emissions also contribute significant ly to overall stationary-source emissions from the refinery. Options for reducing sulfur focus on changing crude slates, changing product fractionation, treating the FCC feed or products, and treating other fuel blendstocks. Even in light of the new environmental regulations, which, in most cases, will require increased capital expenditures, refin ers are feeling increased pressure to increase profits and return on investment. The challenge is to meet the new prod uct requirements and at the same time improve refinery prof itability. Diesel may soon be filling the tanks of our sport utility vehi cles, light trucks, and passenger cars. With its better fuel economy, diesel makes an ideal fuel. But before diesel dis places gasoline, it must be reformulated to reduce its emis sions. One of the first steps in reformulating diesel will be to reduce its sulfur content from the current maximum of 500 ppm in the U. S. to probably less than 20 ppm to meet pending U.S.

more

requirements, and from the current limit of 350 ppm sulfur to less than 50 ppm to meet upcoming European requirements Will this reformulation be sufficient? Automobile and diesel engine manufacturers don t think so. They believe that to achieve U.S. market acceptance for light duty diesel engines, consumers will demand higher quality diesel similar to what is available in Europe. As a result, aromatics concentra tion, cetane, specific gravity, and distillation are under scruti ny. Implementation mandates may be just around the corner! With increased demand for diesel, you will be under pressure to find ways of making more high quality diesel from your existing gasoline oriented refinery. Flexibility will be essen tial and UOP has the distillate technology to provide you with this flexibility. Maximum Quality Distillate (MQD) Unionfining is a family of processes that upgrades difficult diesel blendstocks, such as light cycle oil, into valuable highquality diesel. MQD Unionfining is an integrated approach that can be tailored to meet your specific needs and enable you to produce more high-quality diesel. The Partial-Conversion Unicracking process enables you to produce low-sulfur, high-quality diesel while at the same time improving FCC yields and reducing FCC naphtha sulfur so that it can be blended directly into your gasoline pool. With the PartialConversion Unicracking process, you now have the flexibility to meet the demand for more higher-quality diesel while simultaneously meeting lower gasoline sulfur requirements. Diesel Fuel: Specifications and Demand for the

21st Century

FCC Light Cycle Oil: Liability or Opportunity?

AM-00-28
By Odette T. Eng Technology Manager Distillate and Resid Technologies James E. Kennedy Manager Distillate and Resid Technologies

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FCC Light Cycle Oil: Liability or Opportunity?

Odette T. Eng, and James E. Kennedy UOP LLC Des Plaines, Illinois

INTRODUCTION

With a global shift toward higher quality fuels refiners must address qualities such as aromatics, density and cetane as well as sulfur to meet the changing fuel regulations. One of the largest drags on the quality of the diesel pool today is the FCC Light Cycle Oil (LCO). LCO is high in aromatics, high in density and low in cetane. As refiners gasoline to diesel product ratio moves toward diesel and as lower quality heating oil is upgraded to the required transportation diesel, LCO must be upgraded. In the past we have talked about the synergy between the FCC and FCC Feed Pre-treating units to improve refinery profitability while producing low sulfur products1. This paper will focus on the studies that have been performed for upgrading the LCO to provide the refiner with the ability to utilize the LCO as a higher value fuel-blending component. FCC Feed pre-treating, reduces the sulfur in all the FCC products: gasoline, LCO and flue gas. The yield of FCC gasoline is improved and the profitability increases. However, even this processing leaves a refiner with LCO that is too high in aromatics and too low in cetane to be blended completely into the diesel pool. The purpose of this paper is to illustrate that LCO can be changed from a liability to an opportunity in the future diesel market. The following topics will be covered in this paper : Trend in Transportation Fuels Why is LCO a liability? Can it be an opportunity? Treating of LCO as FCC product Treating of LCO as part of FCC feed pre-treatment

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Trend in Transportation Fuels

Quality In the last two years, the US refining industry has been watching and studying the evolving regulatory requirements. Tier II gasoline pools will have to meet 30 ppm sulfur by 2005 and diesel pools will likely have to meet the same requirement or lower by 2007.* Europe and California have indicated that requirements will be stricter in comparable time frames. In general, world wide legislation is requiring implementation of higher quality transportation fuels. In gasoline, not only sulfur level, but also aromatics concentration, benzene level, and volatility have become targets for evaluation in the drive to reduce tail pipe emissions. For diesel fuel, aromatics concentration, cetane number, specific gravity and T-90 distillation have been under scrutiny for the same purpose. The trend in legislated fuel quality will clearly impact refinery operations. Decisions are being made on how to economically meet the tightening specifications.

Quantity At the same time that the quality is being upgraded by refiners there are projection2 that diesel fuel demand will rise in the future with the wider use of diesel engines in the light duty vehicle fleet. To satisfy the higher demand for higher quality diesel, the refiner must look at ways to increase diesel supply faster than gasoline. In other words the gasoline to diesel ratio of the refiners product demand is projected to change. Upgrading low quality cutter stocks or heating oil to high quality diesel will be required. Currently, existing refining capabilities in the US will not be adequate to cover the demands of Tier II regulations. It is estimated that the refining industry will have to spend a large amount of capital on new facilities. Two issues are paramount to the industry: How to turn a required expenditure with no return into an investment with reasonable payout. How to plan wisely for Tier II - 2005 gasoline specifications and minimize further expenditures to meet Tier II 2007 diesel specifications.

Although there is not yet a firm ruling on the maximum sulfur level for diesel at this time, the EPA has considered a range of 5 ppm to 50 ppm sulfur in diesel for their evaluation. AM-00-28 3

What about LCO?

The Liability Light Cycle Oil, a by-product from catalytic cracking, is normally high in sulfur, nitrogen and particularly in aromatic content. This material, usually in the same boiling range as diesel, can be used as a diesel blending component only after hydrotreating. If future requirements dictate that the diesel pool needs to meet a high cetane number, hydrotreating alone will not be sufficient to upgrade LCO. LCO, rich in multi-ring aromatics, will inherently produce fuel with very low cetane numbers. This is illustrated in Fig.1, where multi-ring aromatics normally found in LCO have cetane numbers ranging from the high teens to the mid twentys.

Figure 1. Cetane Number of Distillate Hydrocarbon Type

100 Cetane Number 80 60 40 20 0 5
le-r Sing

s fin f a ar n-p ns efi Ol

fins araf p o is
es then h p a ing n
T

Aromatics

Decalins etralins

lenes Naphtha

10

15 Carbon Number

20

25
UOP 3300C-1

Upgrading LCO to higher cetane number material requires hydrogenation of multi-ring and single ring aromatics into saturated components and then opening rings. Hydrogenation can take place through severe desulfurization, aromatic saturation and/or hydrocracking. If facilities are not available to upgrade LCO, the refiner will have to divert LCO to maintain cetane. Less valuable products such as fuel oil cutter stock or heating oil are the normal streams. As recent trends indicate fuel oil demand is decreasing3, the cutter stock outlet for LCO will also be decreasing. The problem does not stop there. As more catalytic cracking units are being pushed in octane and capacity due to a general increase in gasoline demand in the last few decades, LCO material produced has increased in multi-ring aromatic content making it lower in cetane and more difficult to upgrade.

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The Opportunity Traditionally, LCO has been upgraded through hydrotreating for diesel blending or through full conversion hydrocracking for high quality naphtha with ultra low sulfur. The requirement for high quality diesel with low sulfur and high cetane adds a new constraint. The opportunity is to keep the LCO in the diesel boiling range and meet the new diesel pool specifications. LCO upgrading needs to be addressed as part of the overall refinery product sulfur strategy. Two distinct options will be explored: the product treatment scenario where each refinery product is individually controlled for sulfur and quality; and the feed treatment scenario where product quality is controlled indirectly through feed quality. In the case of product treatment for an FCC Unit, each product must be treated; gasoline, LCO and flue gas and the clarified oil must find an acceptable home. The control of each product is distinct but it involves numerous units. A simpler alternative is the second scenario where the refiner treats the feed to the FCC Unit and indirectly controls the quality of all of the products in a single unit. The following are two of UOPs novel approaches for LCO upgrading and conversion: MQD Unionfining and Partial Conversion Unicracking.

MQD Unionfining Process

The Maximum Quality Diesel (MQD) Unionfining process includes a suite of processes aimed at the upgrade of difficult, refractory diesel-range material to convert them into high quality diesel meeting required specifications. For the specific purpose of upgrading LCO, cetane index is the controlling quality to be improved by the MQD Unionfining process. The process combination used for any given case depends directly on the product requirements. The product qualities of pour point, cloud point, T-95, aromatics content, density and cetane can all be addressed in an optimized manner depending on the refinery setting. For the upgrading of LCO to make diesel product two alternatives are considered in this paper: Medium pressure single-stage MQD Unionfining unit using base metal catalyst. Low pressure two-stage MQD Unionfining unit using noble metal catalyst.

The choice of which of the above process schemes to use depends on the desired improvement in cetane index (and therefore the amount of aromatic saturation that is required), and on the existing limitations at the refinery.

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High desulfurization activity and high tolerance to H2S and ammonia characterize base metal catalysts. However, they have limited aromatic saturation activity. At a fixed pressure and space velocity, the higher the aromatic saturation activity the lower the operating temperature would be. As the temperature increases, the desired aromatic saturation can become equilibrium limited, as seen in Figure 2. To compensate for this temperature effect, the operating pressure of the base metal catalyst system is increased to improve the catalyst saturation capability. The answer to low pressure aromatic saturation is high activity noble metal catalyst. The hydrogenation activity of noble metal catalysts is far superior to that of their base metal counterparts. However, to maintain their intrinsic high activity, noble metal catalysts need to operate in a low ammonia, low H 2S environment.

Figure 2. Aromatics Reduction Limits at 700 psig

40 Base Metal

Aromatics, vol-%

30

20

10

Kinetics Controlled 450

Noble Metal 600

Equilibrium Constrained 750

UOP 3300C-2

0 300

Temperature, F

MQD Unionfining Process Flow Scheme The preferred reactions in an MQD Unionfining unit have two common aspects. They all consume hydrogen, and they are all exothermic in nature. Because these aspects have a major effect on catalytic performance (conversion, selectivity, and stability), temperature control is a vital consideration in the process design. Cold recycle gas (quench gas) is injected in the reactor at one or more points (between catalyst beds) to control the temperature rise caused by the exothermic reactions. Proper design of the reactor internals ensures safe, controllable operations and maximum catalyst performance. UOPs state-of-the-art reactor internals include an inlet diffuser and vapor-liquid distribution tray for the proper distribution of reactants to the first catalyst bed and a quench zone design between catalyst beds. The quench zone design provides intimate mixing of the reactants leaving the catalyst bed with the quench gas and effective redistribution into the subsequent catalyst bed. These reactor internals minimize any channeling or development of thermal gradients (hot spots) in the catalyst beds. The resultant plug flow distribution pattern and optimized temperature control directly translate to maximum product quality and catalyst life.

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The process flow scheme for the MQD Unionfining process with base metal catalysts is similar to that of a single stage hydrotreater designed for desulfurization. When a noble metal catalyst is specified UOP utilizes a two-stage MQD Unionfining unit. Developing a single unit design with maximum heat integration has minimized capital and operating costs of UOPs two-stage MQD unit. This low-cost, integrated, two-stage design was developed by a joint effort between UOP and Lurgi. A dramatic 40% reduction in both capital and utilities costs was achieved with the integrated design. The two reaction stages have been integrated into a single gas loop with interstage gas stripping to remove contaminants. Thus, once the feed is pumped to reaction pressure, it is not let down until the diesel product is recovered. Along with the single gas loop is a single high-temperature loop, where intermediate heat input is provided solely by process fluid heat exchange. Thus, only a single fired heater and one stage of product cooling is required before the fractionation to generate the net products from the unit. The process flow through the first reaction stage is essentially identical to the single-stage flow scheme for base metal catalysts. After heat exchange, the first-stage reactor effluent enters a pressurized stripper, where recycle gas is used to strip H2S, NH3, and light ends from the hydrotreated liquid. The stripper overhead is further cooled and washed with condensate to remove ammonia salts, which could otherwise foul the final air-effluent cooler. The cooled effluent stream is then flashed in a cold HPS. The flashed gases are directed to an amine scrubber to remove H2S and are then directed to the suction drum of the recycle gas compressor. The hydrotreated liquid exiting the hot stripper again exchanges heat with the first-stage effluent and is combined with recycle gas prior to entering the second reaction stage. The heat of reaction from the second reaction stage is again recovered from the effluent via exchange with the combined reactor charge. The second-stage effluent is then further cooled, flashed, and stripped. A second stage reactor added to an existing hydrotreater makes the low pressure twostage MQD Unionfining process a good fit for revamp situations where existing low pressure distillate hydrotreaters are inadequate to meet the higher quality product requirement. Figure 3 shows the flow scheme of a two-stage MQD Unionfining unit. The second stage has been highlighted and shows how the retrofit could be achieved. The same synergy also makes the two-stage MQD Unionfining unit an ideal candidate for staged investment, whereby the second stage can be added at a future date when cetane improvement is required.

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Figure 3. Low Pressure Two-Stage MQD Unionfining

Figure 3. Treating Option Low Pressure two-stage MQD Unionfining

RG Compressor Makeup Gas First Stage Reactor Hot Quench Stripper Gas Wash Water Second Stage Reactor Stripping Gas Stripped Oil Amine Scrubber Lean Amine Rich Amine HPCS Oil to LPCS

Reactor Charge Furnace

Water

Quench Gas

Feed

UOP 3300C-3

MQD Unionfining Catalysts Hydrotreating UOP has a variety of state-of-the-art hydrotreating catalysts. When the objective is maximum desulfurization with minimum hydrogen consumption, a cobalt-molybdenum (Co-Mo) catalyst is used. When the objective is deep hydrotreating for maximum aromatic saturation, a nickel-molybdenum (Ni-Mo) catalyst is used. Aromatics Saturation When significant cetane upgrading is required beyond what can economically be achieved with base metal catalyst, AS-250 catalyst is used in the second stage of the two-stage MQD Unionfining process. The AS-250 catalyst is a noble metal catalyst using a proprietary support designed for deep aromatic saturation and selective hydrocracking.

Partial Conversion Unicracking

Due to seasonal changes, there are periods of time when distillate is in high demand. This market drive forces the refiner to adjust unit operations to increase distillate production at the expense of gasoline make. This change in operation could be handled through the design of the FCC feed pre-treater operating in concert with the FCC. Previous work by UOP1 demonstrated that the synergy between a FCC and the feed pretreating units can be best realized by stepping up the design of the FCC feed pre-treater to
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that of a partial conversion hydrocraker. The same philosophy and flow schemes would be applied here while upgrading LCO. Conventional partial-conversion hydrocracking flow schemes are similar to fullconversion hydrocracking schemes except that the operating pressure is in the range of 1,500 psig instead of 2,000 to 2,500 psig. Distillate product quality is somewhat lower because of the lower pressure. In addition, distillate product quality is limited by the degree of conversion that can be achieved because the bottoms product from the hydrocracking unit is a feed to another unit. Although higher conversion can be achieved in partial-conversion units that are integrated with FCC units, this conversion is achieved at the expense of feed to the FCC unit. New Flow Scheme The flow scheme in Figure 4 uses two parallel reactors and separates hydrotreating and hydrocracking into distinct reaction zones so that not all of the fresh feed is required to go through the hydrocracking reactor. This design feature is extremely important and only possible because of the two reactor design.

Figure 4. Parallel Flow11. Partial Conversion Unicracking Unit Figure Parallel Flow

Partial Conversion Unicracking Unit

LCO Fresh Feed

R2

R1
Fractionator

Light Naphtha Heavy Naphtha Kerosine

FCCU

Diesel Bottoms LCO

Gasoline

UOP 3300C-13

The two reactor design in this flow scheme provides much greater flexibility than a single reactor design because the fraction of feed that is hydrotreated and the fraction that is hydrocracked can now be customized to meet the specific needs of the refinery. Poorquality streams, such as LCO and heavy cycle oil (HCO), can be upgraded by sending them to either Reactor 1 or 2, depending on the product quality targets.
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The severity in Reactor 1, the hydrotreating reactor, is set primarily by the target sulfur content in the unconverted oil product. The severity in Reactor 2, the conversion reactor, is determined by the distillate quality requirements. Sending only part of the feed to Reactor 2 allows the second reactor to operate at the conversion needed to meet the required distillate product quality. However, the conversion from the overall process is not so high as to deprive the FCC unit of feed. The key to achieving high product quality at low overall conversion is separating the hydrotreating and hydrocracking functions into separate reactors. Using conversion to achieve product quality is more cost-effective than using high-pressure. This new partial-conversion Unicracking options offer flexibility to meet market demands for high-quality middle distillates. This flexibility can also be used to vary the production between gasoline and diesel. High-activity Unionfining catalysts and a wide array of catalysts give refiners the means to customize the product slate to a much greater extent than was possible before. There is a clear advantage to this flow scheme as it offers many possibilities, among which is the potential of staged construction where the second reactor train could be built at a later date. Based on a similar concept, existing units could be revamped to have the second reactor added for quality improvement or product ratio adjustments.

Solution Evaluations
The only way to truly evaluate any technology change is to look at its impact on the refinery. A high conversion US FCC and coker based refinery of 125,000 bpsd was chosen as the basis. The crude slate is a blend of 25% light Arabian, 25% heavy Arabian and 50% Venezuelan. In these examples, gasoline and diesel pools are both required to meet 30-ppm sulfur specifications. In addition there is a future requirement of 50 cetane index on the diesel pool. Fuel oil will be made up of slurry oil and LCO which can not be blended into diesel or lighter products. In order to accurately follow the impact of various processing options REFINE, a nonlinear refinery modeling and blending program licensed by UOP, was used to perform the evaluations. Two situations were examined. In the first, the refiner had already decided to minimize his investment by post-treating the FCC products. In these cases a UOP/Intevep ISAL unit was chosen to remove sulfur from FCC gasoline while retaining octane4. The remaining issue is reduction of diesel sulfur. A diesel hydrotreater to remove sulfur is the required investment. Alternatives are compared with this as a basis.

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In the second situation the refiner has decided to attack gasoline and diesel specifications, and flue gas SOx at the same time, as well as to seek a positive overall ROI. In this set, an FCC pre-treater (VGO Unionfining unit) is the base investment. Alternative technology options are compared against this basis to maximize return on investment. For the evaluations, the product values used are provided in Table 1. Table 1 Pricing Basis Product-crude spreads, $/Bbl Gasoline Kerosene Diesel Fuel Oil 8.5 8.3 5.5 (2.5)

Purchased Gas Oil Crude spread, $/Bbl. Hydrogen, $/MSCF

0.5 2.5

Post-Treat Solutions
Diesel Sulfur Reduction A diesel hydrotreating unit, such as a UOP Diesel Unionfining unit is used to process LCO. Because the FCC feed is not treated, LCO produced from the FCC operation in these cases is of relatively low quality, with an API at around 16 degrees. To get to a 30ppm sulfur specification, all distillate streams and the LCO stream will have to be severely hydrotreated. Even at this high severity, low pressure base metal hydrotreating alone will not be able to significantly improve the cetane index of LCO. Table 2 provides an indication of the relative cetane index improvement for simple hydrotreating of the LCO. With desulfurization and the modest improvement that corresponds to the desulfurization, 1,265 bpd of LCO can be blended into the diesel pool. The remainder is directed to fuel oil or other lower added value products.

Increased Cetane In this case, a moderate pressure MQD Unionfining unit is used to hydrotreat the LCO. The MQD Unionfining unit pressure and catalyst types are specified to provide both desulfurization and an additional improvement in the cetane index of the product. This configuration will allow the refiner to add 3,544 bpd of LCO to the diesel pool.
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Maximum Diesel To maximize the production of diesel, a low-pressure two-stage MQD Unionfining unit is used to hydrotreat the LCO. The two-stage MQD Unionfining unit utilizes a noble metal catalyst in the second stage to provide the maximum cetane improvement through aromatic saturation and selective ring opening. This configuration will allow the refiner to add a total of 6,998 bpd of LCO to the diesel pool. Figure 5 shows the units involved.

Figure 5 Post-treat Schemes LP two-stage MQD Unionfining

Figure 5. Post-treat Schemes LP Two-Stage MQD Unionfining
HDS Crude and Vacuum VGO HCGO LCGO FCC LCO Diesel Gasoline ISAL

Gasoline

Coker

LP MQD Fuel Oil

Diesel
UOP 3300C-7

Comparison For refiners that elect to post-treat the LCO it is clear that desulfurization alone does not improve the quality of LCO enough for a significant portion of it to be used in the diesel pool. Utilization of a moderate pressure MQD Unionfining unit resulted in an improvement in the cetane index of the treated LCO when compared to the base case. However, the level of aromatic saturation at moderate pressure, using base metal is limited by equilibrium temperature. To overcome this limitation, a two-stage MQD Unionfining unit with noble metal catalyst in a second-stage reactor was used. Better aromatic saturation allows the maximum use of LCO in the high quality diesel pool, as can be seen in Figure 6. Table 2 provides a summary of the cetane improvement for the three post-treat scenarios discussed in this section. The cetane index improvement of LCO for this case was superior when compared to the other post-treat scenarios.

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Table 2 Cetane Improvement

Objectives HDS Increased Cetane Maximum Diesel

LCO Feed, Cetane Index Treated LCO Product, Cetane Index

24 30

24 42

24 46

Figure 6. LCO Disposition

10000 9000 8000 7000

Product, bpsd

6000 5000 4000 3000 2000 1000 0 HDS MP Single Stage MQD LP Two Stage MQD LCO to Diesel LCO to Fuel Oil

Figure 7. Overall Refinery Product Distribution with FCC Product Post-Treating

120000 100000 80000 60000 40000 20000 0 HDS MP Single Stage MQ D LP Two Stage MQ D G asoline Ke rose ne Die se l Fue l oils

Figure 7 above summarizes the overall refinery product distribution in the three cases evaluated. It shows that diesel production is progressively increased at the expense of fuel oil in each case.
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The economics comparing the three post-treat scenarios, utilizing the basic simple payback method, indicates that the moderate pressure MQD Unionfining unit required only a moderate increase in capital when compared to the base case, resulting in a simple payback of approximately 0.8 years compared to base hydrotreating case. While the twostage MQD Unionfining unit that utilized noble metal catalyst may have cost slightly more, the incremental payback for this case was only 0.5 years. This data is summarized in Table 3. If a refiner elects to utilize post treating of the FCC products, and at the same time wants to utilize more of his LCO as a high value diesel product, it is clear that he should consider a moderate incremental investment in order to maximize his use of LCO as diesel fuel. If the refiner is not yet ready to concede that the cetane requirement will be going up, then a phased investment approach that includes the future addition of a noble metal second stage can be considered.

Table 3 Summary of Post-Treatment Cases

Objectives HDS MP Single-stage MQD Unionfining Upgrade LCO 30 ppm 30 ppm 50 ISAL MP Singlestage MQD UF LP Two-stage MQD Unionfining Upgrade LCO 30 ppm 30 ppm 50 ISAL LP Two-stage MQD UF

Gasoline Sulfur Target Diesel Sulfur Target Diesel Cetane Index Post-treat processes:

30 ppm 30 ppm 50 ISAL Diesel HDS

Overall Refinery Product Distribution, BPD: Gasoline Kerosene Diesel Fuel Oil (CSO+LCO) Chemical H2 Consumption, MMSCF/D Diesel HDS or MQD capacity, BPD Capital Investment, $ MM Simple Payback, yrs

65,861 5,989 29,608 11,851 Base

66,226 5,989 31,899 9,728 + 4.2

66,346 5,989 35,343 6,369 + 7.5

8,600 Base Base

8,600 + 4.6 + 0.8

8,600 + 6.3 + 0.5

(Incremental values are increments over corresponding Base values)

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Pre-treat Options
Another crucial factor to overall sulfur management and LCO upgrading not yet discussed in our evaluation is FCC feed pre-treatment. Treating of the FCC feed opens up an array of benefits that can not be offered by post-treating. Having the ability to control the quality of the FCC feed through feed treatment allows the refiner to produce materials that meet the stringent environmental demands and more importantly to alter the product ratio and yields to fit the changing market demand. Investments that improve yields and operation are the investments that can produce a return. These are investments aimed at a longer range strategy. FCC feed pre-treatment can help produce on-spec sulfur in gasoline, help meet SO X flue gas emissions and reduce sulfur content in LCO. All this can be done in one unit as opposed to having a specific treating unit for each of the FCC products. While the function of pre-treating is to desulfurize the feed to the FCC, this step will also add enough hydrogen into the feed to make it more paraffinic and easier to crack. As a result, conversion in the FCC toward gasoline will increase at the expense of LCO and slurry oil. Even with the lower amount of LCO produced, there are additional ways to further improve LCO quality by using the FCC feed pre-treater unit. There are instances where the refiner would like to have the flexibility to change the product ratios to match seasonal demands, typically a higher need for gasoline production in the summer and conversely a higher need for distillate production in the winter. The right design of the FCC pre-treater will give the refiner that flexibility and the ability to control conversion including that of LCO into high quality gasoline or diesel. In the following sections, various process options with specific objectives will be evaluated and compared against the basic FCC feed pre-treatment case where the main target is to meet sulfur specifications only. Except for the base case, where no attempt will be made to upgrade LCO, all subsequent cases address the LCO conversion issue. Desulfurization Case Maximum Gasoline Production Case Flexible Gasoline/Diesel Production Case Flexible Gasoline/Diesel Production Case with expansion

Desulfurization The FCC pre-treater feed in our example contains 2.35 wt% sulfur. As both gasoline and diesel will be produced from this pre-treater/FCC system, both products will have to meet the required level of 30 ppm. However, the diesel sulfur target will be more difficult to meet. To avoid having the design of the FCC being controlled by the diesel sulfur target, several flow schemes have been proposed by UOP to solve this problem either through a VGO/Diesel integrated flow scheme or by sending this diesel to a finishing step5. The
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VGO/Diesel Unionfining integrated flow scheme is based on the same concept as UOP patent of several years ago in the area of resid hydrocracking. The overall flow scheme for this case is shown in Figure 8. The nominal desulfurization severity for this operation will be around 99%. Thanks to this high severity and the amount of hydrogen added to the feed, LCO produced from the FCC operation in this case is of relatively good quality, with API ranging from 19-20 degrees, and a low sulfur content in the range of 300-400 ppm. However, the cetane index of the LCO material from this option would only be marginally improved: LCO produced from the treated FCC feed would have a cetane index of 27, a rather small improvement from a cetane index of 24 with an untreated feed. With this quality, LCO would probably be used as low sulfur fuel oil and will not be able to be blended in the diesel pool. Just as in the base case for post-treatment where the process target is only for desulfurization, the base case for pre-treatment results in little upgrade of LCO. The first column in Figure 12 provides a representation of the Refinery yields for this case.
Figure 8. FCC Feed Pre-treater at 99% HDS

Figure 8. FCC Feed Pre-treater at 99% HDS

Diesel Diesel Gasoline

HDS Crude and Vacuum HDS

LCGO HCGO

FCC
LCO

Gasoline Gasoline

Coker

Diesel
Fuel Oil
UOP 3300C-10

Maximum Gasoline Production There are situations where the refiners goal is to maximize the production of gasoline. The natural thought would be to find ways to turn LCO into gasoline. The easiest option would be to recycle LCO back to the FCC for re-cracking. However, two things are required: LCO needs to be hydrotreated before being sent back to the FCC. This saturates the poly-aromatics and makes LCO easier to crack in the FCC. This is accomplished by having LCO re-processed through the FCC feed pre-treater.

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To control the build up of mono-aromatics which are more difficult to saturate in the hydrotreater and thus will remain un-cracked in the FCC, a purge stream of LCO produced from the FCC is required immediately downstream of the FCC.

Figure 9. FCC Feed Pre-treater at 99% HDS

HDS Crude and Vacuum HDS LCGO
HCGO

Diesel Gasoline FCC LCO

Gasoline

Coker

Diesel
Fuel Oil
UOP 3300C-11

Figure 9 represents a flow scheme that can be utilized by a refiner designed to maximize gasoline production, meet gasoline sulfur specifications (30 ppm) and upgrade LCO into gasoline. Similar to the basic FCC feed pre-treating case, this pre-treater upstream of the FCC unit also operates at a nominal 99% desulfurization to keep the sulfur in the FCC gasoline below 30 ppm. If this is a new unit, the FCC feed pre-treater design will need to accommodate for the additional LCO stream. Since the intent of this flow scheme is to maximize gasoline production, all diesel and gas oil boiling material will be kept as feed to the FCC where they will be converted to gasoline. With no diesel production, the desulfurization level for the pre-treater will be controlled by the gasoline sulfur specification only and diesel cetane index will no longer be a concern. As the FCC feed gets pre-treated, the additional hydrogen in the feed will enhance conversion in the FCC and will reduce the amount of LCO and slurry oil produced. Typically, the amount of LCO recycled back to the pre-treater will be equivalent to about 10% of the pre-treater feed, a fairly small amount to accommodate in the design of the new pre-treater. Most of LCO poly-aromatics would be saturated in the FCC feed pre-treater. However, the amount of LCO that can be effectively upgraded is limited due to the net drag stream of LCO pulled from the unit to control the potential buildup of aromatics in the system. This drag stream will have about the same quality as that of the LCO shown in the base case and therefore can be used to blend with low sulfur fuel oil. Compared to the basic feed pre-treating, more hydrogen will be consumed in this case for the partial saturation of the LCO. The capacities of both the pre-treater and the FCC unit will also be increased by about 10% to accommodate for the LCO recycle rate. The improved FCC conversion coupled with the high FCC capacity results in a marked increase in gasoline production. The second column in Figure 12 clearly shows the improved gasoline production, as well as the reduced fuel oil make. Approximately 70%
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of the LCO produced will be converted to gasoline. This scheme has an attractive incremental payout of 1.5 years when compared to the FCC pre-treater scheme.

Flexible Gasoline/Diesel Production In situations where the refiner does not have a crude expansion and needs to keep the FCC full, conversion in the hydrocracking unit needs to be kept at a low level. LCO can still be used as feed to the hydrocracking unit. However, cracking has to be done selectively to try to convert as much LCO into naphtha as possible, so that less of the LCO material will end up in the distillate product where it could adversely affect the distillate cetane index. LCO, though highly aromatic, can be easily cracked in the hydrocracking unit and the produced naphtha will have high octane numbers. The selective cracking can be accomplished with a parallel reactor flow scheme as shown in Figure 4 under the discussion section of partial conversion section.

Figure Partial Conversion Unicracking Figure10. 10. Partial Conversion Unicracking

Diesel Diesel Gasoline HC LCGO
HCGO

HDS Crude and Vacuum FCC LCO Coker

Gasoline

Diesel
Fuel Oil
UOP 3300C-12

To avoid over-cracking other gas oil material, and to maximize conversion on LCO in order to get the highest upgrade on this low cetane component, LCO will need to be processed in a separate parallel reactor. The effluent material from the two parallel reactors can be mixed before going through a common heat exchanger train and a common product recovery section. The small amount of naphtha produced from cracking can be sent to the reformer. Diesel material produced from the partial conversion Unicracking unit can reach a cetane index of 48-49 and therefore can be totally blended with the rest of the refinery diesel pool (51) to make the cetane index of 50. The results for this scheme is shown in the third column of Figure 12. In this case, all LCO has been upgraded to either gasoline or diesel products. The net major gain is in the distillate production with only a marginal increase in gasoline production. This is caused by the drop in FCC feed capacity due to the partial conversion in the Unicracking unit.

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Flexible Gasoline/Diesel Production with expansion For cases where the refiner is planning for a crude expansion but is bottlenecked at the FCC, hydrocracking upstream of the FCC has been the solution to generate additional high quality products (mostly distillates), reduce the feed to the FCC, and avoid revamp work on the FCC unit. As conversion is kept low, distillate will be the main product from this process, usually with reasonably high cetane index. However, by adding LCO as feed, this low cetane material will tend to drag down the cetane index of the distillate produced from this unit. Normally, a higher hydrocracking conversion level will solve this problem. However, higher conversion in the hydrocracker will result in lower feed to the FCC.
Figure 10a. Partial Conversion Unicracking

Figure 11. With Expansion Partical Conversion Unicracking

Diesel Diesel Gasoline HC LCGO
HCGO

HDS Crude and Vacuum FCC LCO Coker

Gasoline

Diesel
Fuel Oil Purchased Gas Oil
UOP 3300C-12A

In order to demonstrate the versatility of the partial conversion Unicracking/FCC system and its ability to produce different gasoline/diesel product ratios, this example uses purchased gas oil as additional feed to the system to get full utilization out of the FCC unit. The same partial conversion configuration will be used. Just as in the previous example, all LCO will be converted to either gasoline or diesel products. However, with the supplemental feed, the FCC will be able to produce more gasoline, as shown in the fourth column in Figure 12. Though the partial conversion cases utilize the most hydrogen in the three (3) examples discussed (Table 4), they have the great benefit of turning all LCO into either high quality gasoline or diesel and also reducing the production of slurry oil through better hydrogenation of the FCC feed. The overall refinery product distributions for each case are shown in Figure 12. The amount of fuel oil reduction from the base FCC feed pre-treating case is shown in Figure 13.
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Figure 12. Overall Refinery Product Distribution with FCC Feed Pre-Treating
160000 140000 120000 100000 80000 60000 40000 20000 0 HDS Maximum Gasoline Flexible Gasoline/Diesel Flexible Gasoline/Diesel with Expansion

Gasoline Kerosene Diesel Fuel oils

Figure 13. Fuel Oil Production with FCC Feed Pre-treating

8000 7000 6000 5000 4000 3000 2000 1000 0 HDS M a xim um G a so line F lexible F lexible G a so line/D iesel G a so line/D iesel with Expa nsio n

F u el o ils

Comparison Table 4 summarizes the results in the pre-treatment cases. These examples demonstrated that desulfurization alone to 30 ppm level, as shown in the base case, does not improve the quality of LCO enough for it to be used in the diesel pool. There is a good potential for LCO upgrade with the use of the LCO recycle stream through the feed pre-treater. However, this case is marginally limited because of the loss of value in the required LCO drag stream. The incremental cost for this case compared to the base case is modest and the expected payback is about 1.5 years. The partial conversion Unicracking cases have the best chances of converting all the LCO into transportation fuels and have the highest flexibility in handling product ratio adjustments. Although the incremental cost of these two cases are higher than the previous case, the additional margins realized through the product conversion resulted in better paybacks of 0.9 and 1.1 years respectively for the partial conversion Unicracking cases, with and without purchased gas oil.

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Table 4 Summary of Pre-Treatment Cases

Objectives: HDS only Maximum Gasoline production Flexible Gasoline/Diesel production Flexible Gasoline/Diesel production With Expansion

Upgrade LCO Gasoline Sulfur Target Diesel Sulfur Target Diesel Cetane Index Pretreatment Process: 30 ppm 30 ppm 50 99%HDS for Pre-treatment 30 ppm 30 ppm 50 99% HDS for Pre-treatment

Upgrade LCO 30 ppm 30 ppm 50 Partial (30%) Conversion Unicracking

Upgrade LCO 30 ppm 30 ppm 50 Partial (30%) Conversion Unicracking Purchased Gas Oil 13,000 BPD

Special Feature:

LCO recycle with drag stream

Overall Refinery Product Distribution, BPD: Gasoline Kerosene Diesel Fuel Oil (CSO+LCO) Chemical H2 Consumption, MMSCF/D

66,825 5,989 38,012 6,986 Base

81,264 5,989 28,473 3,636 + 3.5

68,052 5,989 42,851 1,433 + 6.7

79,151 5,989 46,805 1,864 + 15.8

FCC Feed pre-treater or Partial Conversion Unicracking, BPD Capital Investment, $ MM Simple Payback, yrs

44,600

49,200 47,800 57,569

Base Base

+ 11.0 + 1.5

+ 17.9 + 1.1

+ 36.2 + 0.9

(Incremental values are increments over corresponding Base values)

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CONCLUSION

The distillate market is poised to change. Sulfur in on-road fuel will need to come down to ultra low level, while sulfur in off-road fuel will have to meet the 500 ppm mark. The heating and fuel oil market will continue to shrink. At the same time, there is mounting pressure from the engine and auto manufacturers demanding higher quality diesel as diesel engines for light duty begin to displace gasoline engines. In the midst of this evolving market, refiners must find ways to increase profitability while complying to legislative regulations at the same time. Early planning, taking advantage of potential synergistic opportunities can turn low value materials into higher margin products. LCO has long been known as a drag on the quality of the diesel pool. In anticipation for further tightening of transportation fuel specifications, UOP has evaluated the above 7 cases to help clarify the path forward. In both the post-treatment and pre-treatment scenarios, severe hydrotreating will not be able to upgrade a significant amount of LCO to the diesel pool with a cetane index of 50. In both scenarios, a further step would be required to either deeply saturate LCO or crack it to improve its quality. The decision on post-treatment or pre-treatment of FCC LCO depends on the refinery overall sulfur management strategy. However, FCC feed pre-treatment using partial conversion Unicracking is a solution for long term strategy as it offers greater potential for flexibility. It is the ability to control the product ratio offered by partial conversion which would give the refiner a competitive edge and a means to respond to changes in market demand. Incremental cost of upgrading LCO is relatively small compared to the basic case of hydrotreating to meet regulatory specifications. The concept is to use the same facilities already required to meet regulations to upgrade LCO, simplify operation and maximize the return on investment.

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REFERENCES

1. Exploiting synergy between FCC and Feed Pretreating units to improve Refinery Margins and produce Low-Sulfur Fuels AM-99-55 - Scott Shorey 2. US Light Duty Dieselization Scenarios, Arthur D. Little, Inc., Cambridge, MA, 1999. 3. Petroleum Marketing Monthly 1995-1999, Energy Information Administration, Office of Oil & Gas, US Department of Energy, Washington, DC. 4. Meet gasoline pool sulfur and octane target with the ISALTM process- AM-00-52 Nelson P. Martinez, J. Armando Alazar, Jorje Tejada, Edward Houde, Mahesh Anand. 5. The lower it goes, the tougher it gets (The Practical Implications of Producing UltraLow Sulfur Diesel)- AM-00-16 -Bradford L. Bjorklund, Timothy L. Heckel, Neil D. Howard, David A. Lindsay, David J. Piasecki

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