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ADVANCED FCC CATALYST MATRIX TECHNOLOGY FOR REDUCED COKE AND SLURRY YIELDS
By Alfonse Maglio, Group Leader, Petroleum Catalyst Charles F. Keweshan, Development Chemist Rostam J. Madon, Research Associate Engelhard Corporation Iselin, New Jersey And Joseph B. McLean, Executive Technology Specialist Engelhard Corporation Houston, Texas Presented at the 1994 NPRA ANNUAL MEETING March 20-22, 1994 Convention Center San Antonio, Texas
Abstract
Engelhard's new Reduxion line of FCC catalysts have been developed to offer 10 to 20% lower coke versus current catalysts, while maintaining high bottoms upgrading selectivity. Aspects of Engelhard's PyroChem zeolite technology featured in the Precision Catalyst line have been combined with a controlled matrix acidity distribution which maintains sites selective for bottoms cracking while reducing the strong sites which lead to coke and gas formation. Results from pilot unit testing are presented and projections for commercial operations are provided.
Introduction
With the ever increasing demand on refiners to process heavier crudes and maximize gasoline and diesel yields, fluid catalytic crackers are continually pushed to the edge of their operating limits. Maximum gasoline plus diesel yields are often achieved through the use of high bottoms upgrading FCC catalysts that feature active matrices. However, conventional bottoms upgrading catalysts increase the yield of undesirable products such as dry gas and coke. This often pushes the FCCU up against gas compressor or metallurgical limits, not allowing the refiner to take full advantage of the increased gasoline and diesel yield potential. Current catalysts attempt to address these operating limits by minimizing the activity of the matrix. However, this drastically reduces the bottoms upgrading capability and falls far short of the maximum conversion goals. To impart bottoms upgrading performance, many catalysts utilize high alumina matrices which are stable to deactivation conditions(Ref. 1). These matrices effectively pre-crack large feed molecules to small enough fragments so they can enter zeolite cages where they can further crack more selectively to desirable products. However, there has traditionally been some tradeoff in that the cracked molecules can continue to
crack to undesirable end products such as hydrogen and coke. Engelhard has previously been successful incorporating alumina in the matrix to upgrade bottoms, but with improved selectivity to minimize coke and gas formation(Ref. 2, 3). Taking this technology a step further, we have found a unique method to control matrix activity through an engineered matrix acidity distribution which effectively pre-cracks large feed molecules, but minimizes secondary cracking to coke and gas. The new matrix essentially shifts the secondary cracking burden to the more selective zeolite. By combining this new matrix with Engelhard's proprietary PyroChem zeolite technology, the Reduxion series of FCC catalysts delivers slurry yields equivalent to the best bottoms upgrading catalysts, but with substantially reduced coke and hydrogen yields. PyroChem technology has been demonstrated in the industry in Engelhard's Precision series of FCC catalysts, currently in use in over 20 commercial FCC units. PyroChem zeolite ultrastabilization technology reduces the formation of defects compared to conventional stabilization and dealumination processes. PyroChem zeolites have enhanced zeolite stability and accessibility resulting in decreased catalytic coke and gas formation and increased gasoline selectivity. The proprietary Reduxion process makes it possible to combine the new matrix technology with the PyroChem process.
Performance Evaluation
Gas-oil Feedstocks
A variety of gas oils were employed in order to accurately determine the catalytic performance of Reduxion. Engelhard's standard CTSGO-175 oil is a light, clean oil and affords the benefit of a large internal database. However, the absolute coke yields with this oil are relatively low compared to feeds commonly used in today's refineries. Therefore, heavier gas-oil samples were also utilized
in this evaluation, which are more representative of feeds used in current refinery applications. These oils have low Ramsbottom Carbon and basic nitrogen content but higher boiling point distributions. Sulfur content for all of the heavier feeds were similar to each other but roughly four times that of the CTSGO-175 oil. All of the feeds chosen have low metals content. A summary of the gas-oil characteristics used in the study is shown in Table I.
selectivity. Total dry gas is slightly lower, and octane is slightly higher. Also shown is a comparison for a low matrix activity catalyst. The same delta coke and cat/oil changes are projected as for Reduxion, but at the expense of considerable tradeoffs for the low matrix catalyst. Catalyst makeup rate is increased to maintain the base case MAT activity, and higher slurry yield results from the poorer bottoms upgrading selectivity. Additional drops in C4 olefinicity and gasoline octane also result. It may be possible to offset these drops by lowering rare earth for this case, but the additional zeolite required would increase catalyst consumption and/or cost further. This case study clearly shows the potential advantage for a selective matrix catalyst like Reduxion in an air-constrained case. Comparisons for regenerator temperature and/or wet gas constrained units would show similar advantages in potential conversion and/or throughput as a result of Reduxion's lower delta coke, while minimizing the types of tradeoffs typically associated with low matrix activity catalysts. Reduxion, Precision, Dimension and PyroChem are tradmarks of Engelhard Corporation.
References
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