Expand Hydrocracker Operating Window Through Process Equipment, Catalyst System and Operational Design

Greg Wassel, Operations Engineer Stephen Perry, Manager Process Engineering Shell Deer Park Refining Company Kathy Wu, Sr. Tech-service Engineer Raul Adarme, Global Business Manager, Hydrocracking Criterion Catalysts & Technologies, LP/ Zeolyst International, LP Lora Martinez, Hydroprocessing Specialist Shell Global Solutions (US) Inc.

1.

Introduction

As a critical catalytic conversion unit, a hydrocracker can provide refiners flexibility in balancing supply and demand of gasoline and dieseldelivering significant economic benefit without incurring major capital investment. While the typical two-to-four (2 to 4) year hydrocracking catalyst cycles enable refiners to plan for long-term seasonal variations, short-term product demand volatility challenges and adds complexity to the hydrocracker catalyst selection process. Flexible hydrocrackers swing between gasoline and distillate modes by adjusting process operating parameters such as conversion, liquid recycle rate, and product cut points. The flexibility also requires the design of a tailored cracking catalyst system.
Criterion Catalysts & Technologies, LP and Zeolyst International, LP (Criterion/Zeolyst) work as a team with refiners to select and design catalyst systems that drive conversion while supporting the swing between gasoline and distillate modes. The approach focuses on the cycle objectives, technical requirements, and economics in order to improve hydrocracker flexibility. Inputs include feeds to be processed, product cut points, conversion levels targeted, product yields, product qualities, desired catalyst life, unit constraints, hydrogen quality and availability, supply and demand information, plus economics. The designed options for pre-treat and cracking catalyst systems target different degrees of flexibility and performance.

Using customer business models and proprietary kinetic models, Criterion/Zeolyst and the customer refinery team collaborate in evaluating options for optimum conversion levels, desired yields, and product cut points for flexibility and economic benefits over the full cycle. Additional
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evaluations include consideration of retrofitting existing reactor internals with Shell Global Solutions1 state-of-the-art reactor internals to improve liquid distribution for maximum catalyst utilization and to reduce radial delta temperatures throughout the cycle, assuring the catalyst system reliability and performance. [1, 2, 3] As described in this paper, the collaboration of Deer Park Refining Company (DPRC), Shell Global Solutions, and Criterion/Zeolyst (collectively, the team) resulted in improving unit profitability during the 2007 cycle for the DPRC hydrocracker. The combination of the catalyst system, the new reactor internals, and operating strategy enabled DPRC to expand operating window and to generate additional operating profit of tens of millions of dollars while flexibly adjusting to the variable market demand for gasoline and diesel. The results substantiate ready solutions to the dual challenges of more stringent environmental regulations and the changing pattern of market driven product demand.

2.

Catalyst Selection

The hydrocracking unit at DPRC has single stage reactors in a series flow configuration. It converts heavy straight run gasoil (SRHGO) and light cycle oil (LCO) into more valuable products. The 2007 cycle objectives of the DPRC hydrocracker were to increase unit throughput against a gas-making constraint and to have a flexible catalyst system enabling maximization of naphtha or diesel production based on market demands. To meet the cycle objectives, the team worked together to develop technical solutions for the DPRC hydrocracking unit to improve unit and refinery profitability. Besides the base feed case, the team also investigated different feed cases, such as processing more VGO feed to increase diesel production or shifting more VGO feed from the hydrocracker to the FCC unit to increase refinery gasoline production and process additional LCO feed generated from the FCC unit in the hydrocracker, depending on the market demand. Since the unit was mainly constrained by the gas handling capability and pre-treat catalyst cycle life, the team also evaluated different options to reduce gas-make and improve pre-treat catalyst life to expand the unit operating window. The detailed catalyst system selection process for the pre-treat and cracking catalysts is analyzed in the following section.

a.

Pre-Treat Catalyst System

In the previous cycle, the catalyst cycle life for the DPRC hydrocracker was limited by the pre-treat catalyst life. Figure 1 shows how the unit had to process less difficult feeds (Feeds containing higher percentage of 650F minus material) by the middle of the cycle. The refinery had to reduce throughput in the last part of the cycle in order to meet

Shell Global Solutions is a network of independent technology companies in the Shell Group. In this publication the expression 'Shell Global Solutions' is sometimes used for convenience where reference is made to these companies in general, or where no useful purpose is served by identifying a particular company.

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required nitrogen slip and to reach the targeted catalyst cycle life. The pre-treat catalyst cycle life was limited by the bed peak temperature as shown in Figure 2. It can be seen that bed axial delta temperature decreased as the bed peak temperature increased toward end of the run, showing hydrogenation reaction rate was not increased by increasing bed temperature. This is an indication of the reaction being controlled by equilibrium.

Figure 1 Combined Feed Rate and Percent (%) 650F Minus in the Previous Cycle
Figure 1 shows the percent of 650F minus in the combined feed and fresh feed rate in the previous cycle. Percent of 650F minus and fresh feed rate are on the Y axis and days on stream is on the X axis. Toward the middle of the cycle,(point A) the unit had to increase the percentage of 650F minus material and toward the end of the cycle (point B) the unit had to reduce feed rate in order to meet the targeted cycle life.

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Figure 2 Bed Peak Temperature and Bed dT in One (1) of the Pre-Treat Bed in the Previous Cycle
Figure 2 shows bed peak temperature and bed dT in one of the pre-treat bed of the Deer Park hydrocracker in the previous cycle. Bed dT and bed peak temperature are on the Y axis and days on stream is on the X axis. It is observed that bed dT decreased as the peak temperature increased toward end of the run.

The peak temperature and denitrification limitations are a result of aromatic saturation equilibrium. This can be explained as follows: Nitrogen is present in hydrocracker feeds as heteroatoms in poly-ring aromatic compounds. Adjacent aromatic rings must be saturated before these nitrogen molecules can be converted into ammonia and removed. Figure 3 shows one example of how aromatic saturation (ASAT) conversion is affected by temperature and LHSV at constant hydrogen partial pressure [4]. Percent saturation is on the Y axis and temperature is on the X axis. In the low temperature region, LHSV has a big effect on saturation, showing that the reaction rate is controlled by kinetics. In this region, for a given LHSV, an increase in reactor temperature increases aromatic saturation conversion and denitrification activity. It can also be seen that in the high temperature region, as temperature increases, the effect o f LHSV is reduced. Eventually it has no effect, indicating that the reaction rate is controlled by ASAT equilibrium. For the example in Figure 3, aromatic saturation equilibrium becomes the rate-limiting step at a reaction temperature of around 720F for a LHSV of four (4) or 700F for a LHSV of two (2). These temperatures are much lower than the maximum allowable operating
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temperature of the reactor. Therefore, breaking this ASAT equilibrium barrier is an important element of getting the most performance from the hydrocracking unit.

100
90
Aromatic Saturation (Wt%)

80 70 60 50 40 30 20 10 0 600 625 650 675 WABT ( F) Equilibrium LHSV 0.5

LHSV 0.75

Kinetic Region
700

Equilibrium Region
725 750

LHSV 1.0 LHSV 2.0

LHSV 4.0

Figure 3 - Aromatic Saturation Kinetics: LHSV Effect (at Constant H 2pp)

Figure 3 shows how aromatic saturation (ASAT) conversion is affected by temperature and LHSV at constant hydrogen partial pressure. Percent aromatic saturation is on the Y axis, and temperature is on the X axis. In the low temperature region, LHSV has a big effect on saturation, showing that the reaction rate is controlled by kinetics (kinetic region). In this region, for a given LHSV, an increase in reactor temperature increases aromatic saturation conversion and denitrification activity. It can also be seen that in the high temperature region, as temperature increases, the effect of LHSV is reduced and eventually it has no effect, indicating that the reaction rate is controlled by ASAT equilibrium (equilibrium region).

One (1) way to extend the pre-treat catalyst cycle life is to remove the species generated from the aromatic saturation reaction and to shift the reaction toward higher conversion. Criterion/Zeolyst customers have access to special pre-treat catalyst systems to move the pre-treat catalyst operating temperature closer to the metallurgical temperature limit of the hydrocracker while maintaining the required HDN activity of the pre-treat catalyst system. These hydrocracker pre-treat catalyst systems are stacked beds of state-of-the-art alumina hydrotreating catalyst like CENTINEL Gold, ASCENT, or CENTERA, combined with tailored amorphous silica alumina (ASA) catalysts like Z-503, Z-513, and Z-2513 as shown in Figure 4 (pre-treat catalyst portfolio).

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Figure 4 Criterion Hydrocracker Pre-Treat Catalyst Portfolio

The tailored ASA catalysts are nitrogen-tolerant cracking catalysts with enhanced acidity compared to a conventional hydrotreating catalyst, and they have the power to break open saturated ring-compounds. Ring opening is irreversible, so it breaks through the aromatic saturation equilibrium barrier and significantly increases the rate of hydrodenitrification at temperatures above the normal ASAT equilibrium barrier. The DPRC Hydrocracker Cycle Optimization Team designed a stacked bed system in the 2007 cycle to maximize the pre-treat bed operating temperature window for their hydrocracker. Figure 5 shows examples of different customers that are using this technology successfully at different optimum levels of the ASA catalysts in the stacked system. Each hydrocracker has its optimum stacked bed system and Criterion/Zeolyst works with each customer to determine it. From the different options designed and evaluated, the team ofDPRC, Criterion/Zeolyst, and Shell Global Solutions selected a hydrocracking pre-treat catalyst stack system of CENTINEL Gold DN-3300 and ASA Z-503.

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Figure 5 Zeolyst ASA volume in Hydrocracking Pre-Treaters Commercial Loading

Figure 5 shows Zeolyst ASA catalyst in hydrocracking pre-treaters commercial loading. The volume percent of Zeolyst ASA is on the Y axis and type of hydrocracker is on the X axis.

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Figure 6 shows the peak temperature and bed dT of one of pre-treat bed in the DPRC hydrocracker in the 2007 cycle. With the optimized stacked bed catalyst system, this bed was operated at 7F higher peak temperature at end of run compared to the previous cycle. The delta temperature in this bed was healthy throughout the full cycle. In the previous cycle, this bed DT went down as the peak temperature reached the ASAT equilibrium (Figure 2).

Figure 6 DPRC Hydrocracker Pre-treat Bed Peak Temperature and Bed dT (One (1) of the Pre-Treated Beds Loaded with the Stacked Catalyst System in 2007 Cycle)
Figure 6 shows the peak temperature and dT of one (1) of the pre-treat beds in the Deer Park hydrocracker optimized with the stacked hydrotreating/ASA catalyst system. The hydrocracker was able to operate at 7F higher peak temperature in the 2007 cycle compared to previous cycle while maintaining healthy delta temperatures in the bed.

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Figure 7 shows how the DPRChydrocracker feed rate and feed qualities were well maintained throughout the entire 2007 cycle, as opposed to the previous cycle performance shown in Figure 1. The stacked bed system extended the pre-treat catalyst cycle life and allowed the hydrocracker to operate at higher feed rate while processing more difficult feed. This created significant economic benefit for the refinery.

Figure 7 Combined Feed Rate and Percent (%) 650F Minus in the 2007 Cycle
Figure 7 shows the percent of 650F minus material in the combined feed and fresh feed rate in the 2007 cycle. Percent of 650F minus and fresh feed rate are on the Y axis and days on stream are on the X axis. The plot shows that the feed rate and feed quality were well maintained throughout the entire 2007 cycle as opposed to the previous cycle shown in Figure 1.

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b.

Cracking Catalyst System

Criterion/Zeolyst have been leading innovators in hydrocracking catalyst technology for many years. By having an integrated research and manufacturing capability, the companies have been able to create a wide variety of products to meet specific needs of each refiner as shown in Figure 8 below.

Figure 8 - A Portion of the Criterion Hydrocracking Catalyst Portfolio

Figure 8 shows a portion of the Criterion/Zeolyst cracking catalyst portfolio. The middle distillate selectivity is on the Y axis and cracking activity is on the X axis. The cracking catalyst activity is increased from left to right. The distillate selectivity is increased from bottom to top. Z-803 catalyst is a naphtha/distillate flexible cracking catalyst.

In the previous cycles, the DPRC hydrocracker was loaded with Criterion/Zeolyst naphtha selective cracking catalysts, Criterion/Zeolyst Z-863 and Z-753, which worked well for the cycle objectives and refinery economics of that cycle. The 2007 cycle objectives of the this hydrocracker included maximizing unit throughput against its gas-processing capability constraint and to have a flexible catalyst system to produce more diesel or gasoline depending on their relative margins. From the different options designed and evaluated, the team selected a cracking catalyst system using a Z-863/Z-803 stacked
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system. The Z-803 hydrocracking catalyst provides a unique combination of activity and selectivity and operating flexibility. It produces increased heavy naphtha and distillate selectivity compared to Z-753 at constant conversion. This does not come at the expense of increased hydrogen consumption, as the reduced gas make of Z-803 compensates for the increased hydrogen requirement for distillate saturation. The kinetic and economic analysis of the different options showed that the Z-863/Z-803 stacked bed cracking catalyst system provided the flexibility and robustness required by DPRC, and at the same time it reduced gas-make, which enabled the unit to increase throughput at the current gas handling constraint. The team also evaluated the optimal conversion level for maximizing diesel or naphtha yields. Figure 9 shows the operational range for the Z-863/Z-803 catalyst system for the DPRC hydrocracker. This figure demonstrates that there is a gross conversion range for maximum diesel production. The figure also shows that to maximize naphtha yield, the unit can operate at maximum conversion up to its gas-handling limit.

Figure 9 Product Yield vs. Gross Conversion

Figure 9 shows the product yield versus gross conversion. Volume percent product yield is on the Y axis and volume percent gross conversion is on the X axis. The plot shows the gross conversion range at which the unit can operate to maximize diesel production. To maximize naphtha yield, the unit can maximize conversion up to its gas-handling limit.

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Table 1 illustrates the advantages of the optimized catalyst systerm in the 2007 cycle. The volume percentages are presented on fresh feed basis. All other values are relative to the base values. Since the gas make was lower for the Z-803 catalyst, the feed rate to the unit was increased to match the refinerys capacity to handle the gas generated from the hydrocracker. The increase in the feed rate and heaviness of the feed, combined with the increased selectivity of the catalyst, increased the barrels of diesel production by 2,827 BPD on average. This is particularly important when the diesel margin was significantly higher than the gasoline, as shown in Table 2. The diesel margin was $17/bbl higher than the gasoline margin in 2008 based on the petroleum marketing prices released by the Energy Information administration [2]. This flexibility made additional tens of millions dollars for the refinery in 2007 and 2008.
Table 1 - Commercial Data for Switching from Naphtha to Flexible System

Previous Cycle
Cracking Catalysts

2007 Cycle Z-863/Z-803

Z-863/Z-753

Gas Make, vol% Light Naphtha, vol% FF Heavy Naphtha, vol% FF Diesel, vol% FF Unconverted Oil, vol% FF

Base Base Base Base Base

-20 -1.6 +0.2 +1.8 Base

Feed Rate, BPD Diesel, BPD Hydrogen Consumption, scfb

Base Base Base

+4100 +2827 Base

Table 2 EIA Petroleum Marketing Prices for Fuel Year Diesel Fuel Refiner Wholesale Price (yearly

2007 Cents per gallon Cents per gallon 220.3 218.1

2008 299.7 258.4

average)
Gasoline Refiner Wholesale Price (yearly

average)

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3.

Reactor Internals

The performance of a hydrocracker is not only determined by the catalyst system but also by the design of the reactor internals. Uniform gas/liquid flow distribution in the reactor is essential for good catalyst utilization. Also, the configuration of the internals to meet quench requirements in upper beds for gasoline mode and liquid/vapor distribution in lower beds for distillate mode can serve as a key enabler of market responsive, flexible hydrocracker operation. Despite the significance of the internals, many hydrocrackers have poorly designed internals, i.e., conventional or bubble cap distribution trays, that often results in lost performance and substantial lost economic benefit due to poor flow distribution and under-utilized catalyst. During the 2004 cycle, the DPRC hydrocrackers last cracking bed showed high radial delta temperature. The problem was particularly severe toward the end of the run, as seen in Figure 10 below. The high radial delta temperature is generally an indication of a flow mal-distribution, which could lead to the under-utilization of catalysts and the development of hot spots. This can result in higher gas make and poorer product quality. Criterion/Zeolyst worked closely with Shell Global Solutions and retrofitted the original internals with the latest Shell Global Solutions Reactor Internals Technology in the last cracking bed. The new internals consisted of Shell Global Solutions Ultra Flat Quench (UFQ) including PreDistribution (PD) and High Dispersion (HD) trays at the interbed. The use of the UFQ resulted in a total increased catalyst volume and the use of the HD Tray helped to increase catalyst utilization and improve flow distribution. Figure 10 illustrates the improved bottom bed radial delta temperature after installation of the new internals designed by Shell Global Solutions. With the added catalyst volume and improved flow distribution, the unit was able to operate at higher reactor outlet temperature to save feed preheat energy. This hardware modification with the state of the art internals contributed to the optimization of the unit performance in the 2007 cycle stated above.

Figure 10 The Last Cracking Bed Radial Delta Temperature

Figure 10 shows the cracking bed radial dT in the previous cycle and in the 2007 cycle with the cracking bed radial dT on the Y axis and days on stream on the X axis illustrating the improved bottom bed radial dT after the installation of the new internals.

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Figure 11 provides a graphical view of how the unit was able to operate at a higher net conversion range within the fractionator overhead gas handling limit in the 2007 cycle. This improvement was achieved through the combination of a tailored catalyst system, state-of-art reactor internals, and new operating strategy.

Previous Cycle

2007 Cycle

Figure 11 Fractionator Overhead Vapor Production Versus Net Conversion

Figure 11 shows the fractionator overhead vapor production versus net conversion in the previous cycle and in the 2007 cycle. The overhead vapor production rate is on the Y axis and net conversion is on the X axis. This plot provides a graphical view of how the unit was able to operate at a higher net conversion range within the fractionator overhead gas handling limit in the 2007 cycle.

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4.

Conclusions

Guided by a refiners short term and long term goals, Criterion/Zeolysts hydrocracker catalyst system solutions help enable refiners to increase profitability while flexibly meeting the challenges of gasoline and diesel market volatility. The solutions involve complementary state of the art hydrocracking catalysts from Criterion/Zeolyst, the best in class reactor internals from Shell Global Solutions, and partnership with the refinery. Through this collaboration, even during a period of poor refinery margins and industry emphasis on cost reduction, Criterion/Zeolyst succeeded in enabling DPRC refinery to increase hydrocracker revenue by tens of millions of dollars by prioritizing distillate and heavy naphtha products from the hydrocracker operation, reinforced by reduced unit energy costs, by expanding the unit operating window, and by achieving a longer catalyst cycle. The solution for this refiner integrated a stacked bed state-of-the-art catalyst system with Shell Global Solutions ultra flat quench inter-bed internals and high dispersion tray technology. Similar success can be anticipated for refiners seeking market responsive, flexible hydrocracker catalytic solutions.

5.

References
1.
M. Hu, R. Anderson, R. Adarme, C. Ouwehand, and J. Smegal, The Era of ULSD New Challenges and Opportunities for Hydrocracking Processes, NPRA 2006 Annual Meeting, AM-06-46. A. Sharpe, B. Jones, V. Hruska, G. Baumgartner, R. Anderson, R. Adarme, M. Hu, C. Ouwehand and M. Boer, A Success Story: Significant improvement in hydrocracker profitability with ULSD production through customized catalyst systems, state of the art reactor internals and outstanding technical cooperation, NPRA 2007 Annual Meeting, AM-07-67. R. Karlin, A. Macris, and R. Adarme, Dieselization in North America: Flexible Solutions for Diesel Production, NPRA 2009 Annual Meeting, AM-09-10. Deactivation of Hydroprocessing Catalysts: Thermochemistry of Coke Formation, by Paul R. Robinson, presented at the Second International Symposium on Hydrotreating / Hydrocracking Technologies, American Chemical Society National Meeting, San Francisco, California, September 10, 2006. U.S. Energy Information Administration Short Term Outlook on diesel and motor oil prices.

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5.

6.

Acknowledgements

The authors wish to thank and acknowledge the contributions of many colleagues in preparation and review of this paper: Criterion Catalysts & Technologies: Ward Koester, Mike Hu, Paul Robinson, Zoe Stonebraker Shell Global Solutions: Robert Karlin, Aris Macris, Vito Bavaro
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 2010 Deer Park Refining Company, Criterion Catalysts & Technologies, LP, Zeolyst International, LP and Shell Global Solutions (US) Inc. All rights reserved.

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