Optimizing FCC Operations in a High Rare Earth
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August 03, 2011 VOL: 2 ISS: 15 Optimizing FCC Operations in a High Rare Earth Cost Market: Part I Highlights of Recent Grace FCC Webinar Focusing on Unit Operation and Profitability when Re- formulating FCC Catalyst to Lower Rare Earth Higher feed volumes are processed metric ton on the Asian Metal Index, a acid site density and prevents dealumi- through FCC units than ever before, at 2700% increase in price over the course nation. A catalyst designed with a high the same time that more challenging of a year! This is why the industry has RE exchange for high gasoline selectiv- feedstocks have entered the market. demonstrated such a strong response to ity will have more Cont. page 2 The industry has responded with ef- finding solutions to RE inflation. fective catalyst chemistry that has in- Rare earth supplies are expected to In This Issue... cluded adding higher quantities of rare remain in critically short supply until at earth (RE) to the zeolite. However, least 2014, when mines in other parts of FEATURE with the unprecedented inflation in RE the world are fully developed. Lantha- costs, the onus is now on reformulat- Optimizing FCC Operations in a High num (atomic number: 57) is the lightest Rare Earth Cost Market: Part I ing FCC catalysts to lower RE, while of the rare earths as shown on a typical maintaining or exceeding the high lev- Periodic Table of the Elements. Lantha- els of performance achieved by the latest PROCESS OPERATIONS num has been the dominant RE metal ISOCRACKING Technology Update catalyst systems. engineered into FCC catalysts, followed In an FCC webinar earlier this sum- by cerium (Ce), which has been used Refinery Propylene Production mer, Grace Davison’s David Hunt primarily in SOx reduction additives discussed zero and low RE catalyst al- as well as in some NOx reduction ad- INDUSTRY NEWS ternatives and commercial updates, in- ditives. Shanghai Petrochemical Company cluding a case study detailing catalyst’s Increases Refining Capacity impact on operation and profitability at Ensuring High Activity Idemitsu’s Chiba Refinery Increasing a refinery’s FCC unit. Rare earth applications were developed FCC Propylene Production in the 1960s and have provided unique World’s Largest Paraxylene Plant to Future Role of Lower RE Catalysts functionalities to FCC operations by be Built in South Korea The role played by RE-based catalysts way of improved zeolite active site den- Orpic Increasing Heavy Oil Processing over the past 50 years cannot be dis- sity, selectivity and hydrogen transfer, puted. More recently, constrained units as well as to protect the zeolite from Sri Lanka Seeking Foreign Investment have benefited from RE-based catalyst metals deactivation. Initially, RE-free for Major Refinery Upgrade activity, which is effective in mitigating catalysts were developed in the 1980s Qatargas Doubling Condensate reduced residence time in FCC reactors. and 1990s to maximize FCC gasoline Refinery Capacity Nonetheless, recent RE price inflation octane as lead was being phased out of PetroVietnam Dung Quat Refinery compels refiners and their catalyst sup- the gasoline pool and alkylation capac- Restarted pliers to seek other alternative to RE- ity was not sufficient to provide octane based zeolites. requirements. Rare earth based catalysts BP Whiting Refinery Delaying Startup Briefly, 97% of the world’s RE sup- provide high conversion for units that of New Hydrotreater and Coker ply is from China. Since the beginning may be constrained by coke yields or Murphy Oil Refinery Sold to Valero of 2011, RE prices have been highly in- catalyst circulation. flated and there are limited short term The aluminum (Al) atoms within the EDITORIALLY SPEAKING options for supply of RE such as lan- zeolite structure bring about a charge Opportunity Crude Processing thanum (La). For example, lanthanum and balance for acid types on the zeolite. oxide (La2O3) was recently $140,000/ RE exchange increases zeolite active CALENDAR Copyright 2011. Refinery Operations RefineryOperations.com | 2011.08.03 1 August 03, 2011 aluminum atoms (e.g., 16 Al atoms/unit cell; Si/Al = 12; UCS = 24.32 Å) than a catalyst with a low RE exchange for high LPG olefin selectivity (e.g., 7 Al atoms/unit cell; Si/Al = 27; UCS = 24.25 Å). The Al atoms are also slightly larger than the Si atoms. Adding RE to a zeo- lite surface therefore area increases unit cell size (UCS) due to higher acid site density. This increases feed conversion and activity at constant C/O ratio. Cata- lyst circulation limited units of course benefit from a very active catalyst. Units that operate in the 24.30 to 24.34 UCS range produce lower coke per unit of conversion and gasoline. In addition, air blower constrained units operating within this 24.30 to 24.34 UCS range produce higher conversion and activity than (for example) units that that are blower constrained, as compared to FCC units operating at a lower UCS. Refiners are beginning to see the benefits of low rare earth exchange catalyst formulations in Gasoline octane (RON) and olefins de- their FCC units crease with increasing UCS, which was Are we pulling too much RE out of Joann Deady, Vice President of Global important in the late 1990s and early the zeolite? This will be discussed fur- Marketing for Refining Technologies 2000s period when refiners had to meet ther in Part II of the next issue of Re- ([email protected]). olefins limits specified by the US EPA’s finery Operations, as reformulating Complex Model requirements. catalysts to lower rare earth (RE) con- Rosann K. Schiller, Senior Marketing tent have been commercialized, they Manager ([email protected]) Rare Earth Alternatives have demonstrated their ability to pre- A worldwide Ecat database covering the vent dealumination and meet product past decade shows an increasing use of Angela Jones, North America FCC Market- specifications, even in high sulfur and ing Manager ([email protected]). RE from about 2.0 wt% in 2000 to al- resid operations (e.g., 2000 ppm Va). n most 3.0 wt% in 2010. During that same time period, activity and UCS increased while Ecat zeolite surface area decreased. Grace FCC Webinar Speaker In 2011, the industry has actually seen David Hunt, Lead FCC Technical Spe- its first decline in 20 years of RE content cialist, North America (david.hunt@ and UCS. Of course, the rapid increase grace.com). in RE cost has predicated pulling the RE content out of FCC catalyst. Webinar Technical Contributors PROCESS OPERATIONS ISOCRACKING Technology Update Chevron has established several licens- (Surgutneftegaz) is building one of high-quality fuels for Russian and for- ing partnerships for the its proprietary the world's largest ISOCRACKING™ eign markets and produce diesel fuel technology in Russia through Chevron units. The facility, expected to be com- that complies with Euro 5 European Lummus Global (CLG), Chevron’s joint missioned in 2012, is designed with emission standards. venture with CBI/Lummus Technology. an annual processing capacity of 3.0 The energy company Tatneft has li- Licensing Chevron's ISOCRACK- million metric tons of vacuum gas oil censed the ISOCRACKING technol- (VGO). It will enable production of ING® catalyst, Kirishi Nefteorgsyntez ogy for the Taneco Cont. page 3 Copyright 2011. Refinery Operations RefineryOperations.com | 2011.08.03 2 August 03, 2011 Nizhnekamsk refinery, which is under construction. This refinery will manu- facture high-quality diesel and jet fuel. Startup is expected by late 2011 or early 2012. The technology behind Chevron’s ISODEWAXING catalyst was licensed Editor, Rene Gonzalez, to produce base oils at the same refinery. Refinery Operations The base oils facilities are expected to PO Box 11283 start operation in 2013. Spring, TX. 77391 USA CLG has a sales contract with Ros- Mobile: +1 713-449-5817 neft's Tuapse refinery for a hydrocracker Office: +1 281-257-0582 and diesel hydrotreater license. The Fax: +1 281-686-5846 contract also covers a future supply of [email protected] catalysts for the Tuapse refinery. This re- finery will produce jet and diesel fuels. Published biweekly by nEMESIS Media Group, LLC Startup is planned for 2012. Hydro- PO BOX 5416 crackers typically run at high tempera- Kingwood TX 77325. USA ture 650-800˚F (345-425˚C) and very Phone: (713) 344-1379 high pressures of 1500-3000 psi (105- [email protected] 210 bar). Hydrocracker reactors contain Support multiple fixed beds of catalyst typi- Leon de Bruyn, Chevron Lummus Global cally containing palladium, platinum, or Joint-Manager Director Client Support nickel. These catalysts are poisoned by [email protected] sulfur and organic nitrogen, so a high-se- hydrocracking unit license agreement Advertising verity HDS/HDN reactor pretreats feed- with CLG for applying ISOCRACK- stock prior to the hydrocracking reactors. ING technology to the Jazan Refinery Advertising & Marketing Dept. Project that is currently in the front-end [email protected] Hydrocracker units may be configured in single stage or two-stage reactor systems engineering design (FEED) phase. The Group Subscriptions that enable a higher conversion of gas oil CLG licensed hydrocracker will be uti- Client Services into lower boiling point material. lized to convert 106,000 bpd of VGO — [email protected] Chevron also sells hydrotreating from the new 400,000 bpd Jazan refinery — into high quality diesel fuel, meeting Copies & Reprints catalysts and technical support to refin- ers in Russia through Advanced