FCC TECHNOLOGY UPGRADES: A COMMERCIAL EXAMPLE

Authors: S.J. McCarthy - Mobil Technology Company M.F. Raterman - Mobil Technology Company C.G. Smalley - Mobil Technology Company J.F. Sodomin - Mobil Oil Corporation Rik B. Miller - The M.W. Kellogg Technology Company Publication / Presented: AM-97-10 Date:

FCC TECHNOLOGY UPGRADES: A COMMERCIAL EXAMPLE

by

S.J. McCarthy, M.F. Raterman, C.G. Smalley

Mobil Technology Company Paulsboro, New Jersey USA and

J.F. Sodomin
Mobil Oil Corporation Paulsboro, New Jersey USA and

Rik B. Miller
The M.W. Kellogg Technology Company Houston, Texas USA

FCC Technology Upgrades: A Commercial Example

I.

ABSTRACT

The refining industry has become exceedingly competitive over the past 15 years. The net result of competitive pressures has been significant downsizing and rationalization of less profitable refineries. To survive, the remaining refineries must continue to improve efficiency, reduce operating costs, and adopt flexibility to respond quickly to changes in market demands. Also, refineries must implement selective technology upgrades to ensure continued profitability. Fluid Catalytic Cracking is one of the most flexible and profitable refinery upgrading processes. Therefore, a properly equipped Fluid Catalytic Cracking unit has significant potential to ensure refineries remain competitive. Mobil and Kellogg have developed advanced FCC process technologies that are proven mechanically reliable and profitable. This paper highlights selective FCC technology upgrades aimed at debottlenecking an existing FCC unit and improving financial performance. These technology upgrades include: Closed Cyclones to reduce post-riser thermal cracking, stripper modifications to reduce coke make, ATOMAX feed nozzles to improve feed atomization, and radial injection to improve feed and catalyst mixing. Mobils Paulsboro refinery is provided as an example of how selective FCC technology upgrades can improve overall refinery profitability.

II.

INTRODUCTION

Fluid Catalytic Cracking (FCC) is one of the most flexible and profitable refinery upgrading processes. While commercialized more than 50 years ago, FCC has maintained a preeminent position by evolving to meet changing product, environmental and operational demands quickly and profitably. Several recent hardware developments are aimed at debottlenecking unit constraints to improve financial performance. Specific developments include elimination of post-riser thermal cracking, stripper modifications to reduce coke make, and high efficiency feed and catalyst mixing. Successful commercial demonstration of new hardware developments is critical before widespread implementation. Reliability and operability are vital for a refinery to realize the full benefits of new technology. The FCC alliance of Mobil and M.W. Kellogg combines the strength of both companies to ensure the reliability and operability of new technology. Mobil provides both traditional FCC research and development and commercial demonstration of new technologies. Kellogg provides strong process and mechanical engineering capabilities. This paper highlights specific FCC technology upgrades which have proven profitable for both existing and grassroots units. Specific technology upgrades discussed include closed reactor cyclones, new baffle design for high flux strippers, ATOMAXTM feed nozzles, and radial feed injection. Mobils Paulsboro refinery provides an excellent example of how these selective technology upgrades can improve overall refinery profitability. These FCC technology improvements have also been successfully demonstrated at other Mobil and licensee refineries.

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FCC Technology Upgrades: A Commercial Example

III.

BACKGROUND

Mobils Paulsboro refinery provides an excellent case study of how strategic technology upgrades can improve the FCC units contribution to overall refinery profitability. The FCC is a UOP high efficiency unit (Figure 1) built in 1980 and originally designed to process 30 TBD. The FCC feedstock is a mixture of indigenous VGO, purchased VGO, lube plant byproducts, and coker gas oils. These feedstocks are not hydrotreated by the refinery and are a daily challenge to upgrade. Main products are fuel gas, C3 and C4 LPG, gasoline, light cycle oil and slurry oil. Operating strategy is for maximum conversion and is typically constrained by coke burning rate and wet gas compression capacity. Advanced control packages are in use on the FCC, main fractionator, and unsaturated gas plant. The unit was revamped to include Closed Cyclone technology in 1988. Then, in 1995, Paulsboro installed ATOMAX feed nozzles and proprietary FLUX TUBE stripper baffle technology that reduced regeneration air requirements and improved yield selectivity. ATOMAX and FLUX TUBE technologies were jointly developed by Mobil and Kellogg. The FCC unit now processes more than 46 TBD at conversion levels well above 70 vol%. Yield surveys were performed before and after the turnaround to quantify the benefits of the hardware improvements. The impact of each of these technologies is discussed below.

IV.

MOBIL / KELLOGG FCC TECHNOLOGY IMPROVEMENTS

a.

Closed Cyclones

Cracking temperatures above 1000F are common for FCC units operating to produce light olefins and high octane gasoline. At these temperatures, the contribution from non-selective thermal cracking in the reactor vessel becomes significant. The main advantage of catalytic cracking over thermal cracking is lower coke and higher gasoline selectivities. Therefore, it has become imperative to redesign product and catalyst separation systems to eliminate thermal cracking. Many designs to reduce non-selective post-riser cracking have been investigated, developed and commercialized over the past 20 years. They all share the same basic concepts of quickly separating spent catalyst from cracked products, introducing the catalyst into the stripping zone, and minimizing the time product vapors are held at high temperatures. The evolution of FCC riser termination devices is depicted in Figure 2. Early designs favored crude rough cut separators on top of the riser followed by reactor cyclones. In later designs, rough cut separators were replaced by riser cyclones. Although they are more efficient than their predecessors, both rough cut separators and riser cyclones discharge the products into the reactor/disengager. The large volume in this region allows significant thermal cracking to occur at essentially riser top temperature. Analysis shows that about 50% of the hydrocarbons that exit the riser cyclones are backmixed into the reactor vessel. Rough cut separators result in even higher levels of backmixing. The hydrocarbons that backmix undergo unselective thermal cracking resulting in a loss of gasoline and distillate yield and increase in light gas and heavy fuel oil make.

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FCC Technology Upgrades: A Commercial Example

Closed Cyclones essentially eliminate the backmixing in the reactor vessel. This is accomplished by directly connecting the outlet of the riser cyclones with the inlet of the reactor cyclones. With Closed Cyclones only about 3 wt% of the riser products are backmixed in the reactor vessel, mostly due to entrainment of hydrocarbons down the riser cyclone diplegs. Converting unducted riser cyclones to Closed Cyclones typically increases gasoline and distillate yield by about 2.5 wt % while reducing dry gas yield by about 1 wt %. This represents a reduction of 40% in the sulfur-free, dry gas make. Even greater benefits have obtained when revamping units that previously used crude inertial separators1. A refinery may take advantage of the reduction in gas make by increasing cracking severity and conversion. Other refineries may choose to increase feed rate or resid content within a wet gas constraint. Another benefit of Closed Cyclones is the reduction in unwanted byproducts. One such thermal byproduct, butadiene, increases acid consumption in downstream alkylation. Closed Cyclones typically reduce butadiene yield by about 50%. Closed Cyclones were installed on the FCC unit at Mobils Paulsboro refinery in 1988. Tracer tests showed that Closed Cyclones reduced hydrocarbon backmixing in the FCC reactor vessel from about 40 wt % to about 3 wt %. Butadiene measurements after the turnaround were approximately 45 to 50% lower than the pre-turnaround values, demonstrating a significant reduction in thermal cracking. Also, reactor vessel temperatures ranged from 40 to 70F lower than the riser top temperature, again confirming reduced backmixing. Yield surveys before and after the turnaround show that gasoline and distillate yield increased by 2.4 wt % at the expense of light gas and heavy fuel oil (Table 1). At that time, Paulsboros FCC operation was constrained by the refinery fuel gas balance. Therefore, the refinery took advantage of the drop in dry gas make by increasing severity. Despite increasing severity to maximum riser top temperature, the fuel gas yield was still less than without Closed Cyclones. This increase in severity further decreased bottoms yield and increased gasoline octane. Overall, Closed Cyclones provided about a $0.30/bbl uplift.

b.

Feed Injection and Catalyst Mixing

The feed injection system is one of the keys to yield optimization and profitability. Catalytic cracking reactions occur in the vapor phase on the active catalyst surface. Therefore, a well designed feed injection system must provide quick vaporization and intimate contact between catalyst and oil. Poor feed vaporization and mixing create localized regions of high and low catalyst-to-oil ratios and induce backmixing which increases coke. Improvements in feed injection can reduce coke and light gas production, resulting in higher conversion and improved selectivity toward premium products. Gasoline yield increases as high as 5 vol% and conversion increases of over 4 vol% have been observed commercially with the Kellogg/Mobil ATOMAX feed injection system. Rapid feed vaporization requires atomization into small droplets with a narrow size distribution. Smaller droplets vaporize faster than larger droplets. The feed injection system must also efficiently use the available liquid pressure drop to reduce operating costs or provide optimum atomization within fixed feed supply pressure constraints. The spray pattern from the nozzle must evenly distribute the oil within the riser to provide rapid and uniform oil and catalyst mixing. Oil should be sprayed into a dense phase of catalyst to ensure high local catalyst-to-oil ratios. The feed must have sufficient momentum to penetrate the flowing catalyst without causing erosion of the riser wall or excessive catalyst attrition. AM-97-10 Page 4

FCC Technology Upgrades: A Commercial Example

ATOMAX nozzles have been installed on most of Mobils FCC units and have been licensed to more than 32 FCC units to provide superior feed atomization and mixing. The ATOMAX nozzle, shown in Figure 3, was developed jointly by Mobil and Kellogg. Its key features are that steam pressure provides most of the energy for atomization and mixing and, thereby, avoids expensive pressuring of the liquid feed. Simple and reliable internals and a unique discharge cap provide superior atomization, riser coverage and penetration without erosion of the nozzles or riser wall. Atomization is not significantly effected by large changes in feed rate and this compliments various FCC operating strategies. ATOMAXTM nozzles were installed at Mobils Paulsboro refinery during the 1995 turnaround. Paulsboros original feed nozzles were an atomizing tip-orifice type, installed axially at the base of the riser. The new feed injection system consisted of ATOMAX nozzles oriented radially around the circumference of the riser. The new nozzles were designed for higher feed rate and efficiently utilized available feed pressure drop. Yield surveys before and after the turnaround show Paulsboro achieved a 1.3 wt % increase in conversion and a 1.4 wt % increase in gasoline yield with the installation of ATOMAXTM nozzles (Table 1). Improved feed vaporization and oil and catalyst mixing reduced thermal cracking, which reduced the coke and dry gas selectivities and improved the gasoline selectivity. Reduced coke selectivity allowed higher conversion within the coke burning limitations of the unit. Overall, ATOMAXTM nozzles provided a $0.34/bbl uplift, representing about a 3-month payout.

c.

Stripper Baffle Design

The performance of the FCC reactor stripper also has a substantial impact on yields and profitability. Ideal stripper design provides adequate catalyst residence time and low catalyst fluxes to allow steam to flow upward through the stripper. Good stripper baffle and steam distributor design are also essential to good stripper performance. Poor stripper performance results in hydrocarbon vapors being burned in the regenerator. This increases both regenerator temperature and steam partial pressure. Poor stripping also reduces feed rate or conversion in FCC units constrained by air blower capacity. Mobils Paulsboro FCC stripper is an annular design (Figure 4) which operates at relatively high catalyst fluxes. Higher than design feed rates and operating severities have increased catalyst fluxes, resulting in flooding and poor stripping efficiency. Figure 5 depicts the problems encountered in high flux annular strippers. This type of behavior has been observed in cold flow stripper modeling and confirmed in commercial tests. A survey in August 1994 confirmed the stripper problems and, depending on conditions, unstripped hydrocarbon vapor accounted for 10 to 15 wt% of the regenerator coke load. An efficient stripper typically achieves less than 6 wt% unstripped hydrocarbon vapor as a percentage of total coke. Low spent catalyst standpipe density also indicates poor stripper performance because a high percentage of the steam added to the stripper is being entrained with the spent catalyst to the regenerator. In 1995, the Paulsboro refinery installed a new proprietary stripper baffle technology that reduces flooding and improves stripping efficiency. Known as FLUX TUBE baffles, this technology was jointly developed by Mobil and Kellogg. Compared with previous baffles designs, they are extremely efficient in high flux strippers and they significantly increase the operating range without requiring modification of the stripper shell. The performance of conventional and FLUX TUBE baffles is compared in Figure 6. AM-97-10 Page 5

FCC Technology Upgrades: A Commercial Example

FLUX TUBES have been successfully installed at two other Mobil locations and in one licensed unit. The low-cost modifications did not require enlargement of the outside shell of the reactor vessel and did not extend the turnaround duration. Paulsboro FCC Stripper Performance Before and After FLUX TUBE Installation Pre-Turnaround 10 - 15 69 - 78 35 - 50 50 - 65 1365 Post Turnaround 3-5 89 - 93 68 - 78 22 - 32 1335

Hydrocarbon Vapor as a % of Total Coke Relative Stripper Efficiency Steam to Reactor, wt% Steam to Regenerator, wt% Regenerator Temp., F

A survey conducted following the turnaround showed about a 65% reduction in unstripped hydrocarbon vapor entrained to the regenerator at constant stripping severity. The reduced regenerator coke load lowered regenerator temperature by about 30F and provided the flexibility to operate the FCC unit at higher feed rates and higher severity. The lower regenerator temperature, accompanied by a lower steam partial pressure, reduced catalyst hydrothermal deactivation. Equilibrium catalyst activity increased by 3 MAT at constant catalyst makeup rate. Yield surveys before and after the stripper modification show Paulsboro was able to achieve a 1.2 wt% increase in conversion at constant feed rate because of the stripper modifications (Table 1). Correspondingly, gasoline and alkylation unit feed increased, predominantly at the expense of light cycle oil and bottoms. There was a slight increase in dry gas as a result of improved stripper performance. As expected, coke yield increased slightly due to the lower hydrogen content of the coke, with better stripping, which reduced the heat of combustion per pound of coke. Overall, FLUX TUBE stripper baffles provided about a $0.12/Bbl uplift. Also, the operating envelope of the Paulsboro stripper has been sufficiently extended to allow a much wider range of operating conditions.

V.

SUMMARY

The Paulsboro Refinery has benefited from selective FCC technology upgrades all of which came from development programs jointly conducted by Mobil and Kellogg and which are available for license from Kellogg. Most of the FCC technology improvements have also been successfully implemented at other Mobil locations as part of our program to remain competitive. As described above, these technologies have helped Mobils Refineries remain profitable and viable in an exceedingly competitive environment.

VI. 1.

REFERENCES "FCC Reactor Product-Catalyst Separation --- Ten Years of Commercial Experience with Closed Cyclones; R.B. Miller, T.E. Johnson, C.R. Santner, A.A. Avidan, and D.L. Johnson; 1995 NPRA Annual Meeting, San Francisco, CA; 20 March 1995. AM-97-10 Page 6

FCC Technology Upgrades: A Commercial Example

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FCC Technology Upgrades: A Commercial Example

TABLE 1

Paulsboro FCC Yield Improvements: Post Revamp

Yields, wt% H2S Dry Gas Propane Propene n-Butane i-Butane Butenes Gasoline Light Cycle Oil Bottoms Coke

Closed Cyclones 0.0 -0.4 -0.1 0.0 0.3 0.3 0.0 0.8 1.6 -2.6 0.1

ATOMAX 0.0 -0.3 0.1 -0.1 0.1 0.1 0.0 1.4 -0.9 -0.4 0.0

FLUX TUBES 0.0 0.2 0.1 0.2 0.1 0.2 0.1 0.2 -0.8 -0.4 0.1

Conversion

1.0

1.3

1.2

Uplift, $/bbl

0.30

0.34

0.12

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Mobil's Paulsboro FCC Unit

UOP high efficiency unit originally designed to process 30 TBD Feedstocks: Non-hydrotreated
Indigenous and imported VGO Lube byproducts and coker gas oils

Products
Fuel gas, C3 and C4 LPG, and gasoline Light cycle and slurry oils

Strategy: Maximum conversion Constraints: Air blower and wet gas compressor capacities

Figure 1

Evolution of Riser Termination Devices

Inertial Separator
Poor cat alyst /vapor separation Much dilute phase cat cracking High vapor residence t ime (post-riser thermal cracking)

Riser Cyclones
Good catalyst /vapor separation Lit tle dilute phase cat cracking High vapor residence t ime (post-riser thermal cracking)

Closed Cyclones
Excellent catalyst /vapor separation No dilut e phase cat cracking Very low vapor residence time (no post-riser t hermal cracking)

Figure 2
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ATOMAX Feed Injection Technology

Original Mobil Paulsboro feed nozzles were an atomizing "tip-orifice" type, installed axially ATOMAX Feed Injection System
now installed on most Mobil FCC units small, uniform droplets provide rapid feed vaporization efficient use of feed pressure drop uniform spray pattern that penetrates flowing catalyst catalyst lifted to injection zone in dense phase for improved hydrodynamics and heat transfer

Higher conversion and improved product selectivities

ATOMAX Feed Injection System

Figure 3

Figure 4
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Figure 5

FLUX TUBES Outperform Conventional Baffles

FLUX TUBE Baffle
Stripper Efficiency (%)

Baffle "B"

CRITICAL FLUX

Baffle "A"

Superficial Mass Flux (lb/ft/s)

Figure 6
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