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The Development of Rare-Earth Free FCC Catalysts

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The Development of Rare-Earth Free FCC Catalysts April 06, 2011 VOL: 2 ISS: 6 The Development of Rare-Earth In This Issue... Free FCC Catalysts FEATURE Rapid Escalation of Rare-Earth Metal Prices Has Accelerated The Development of Rare-Earth Free Formulation of Rare-Earth Free Fluid Catalytic Cracking Catalysts FCC Catalysts Colin Baillie and Rosann K. Schiller, Grace Davison Refining Technologies PROCESS OPERATIONS Debottlenecking HCGO Filtration Rare-earth (RE) metals are important Grace developed the Z-21 RE-free sta- FCC Ecat Contaminant Levels Maintain for stabilization of the Y zeolite compo- bilized Y zeolite. Based on this devel- Upward Trend nent of FCC catalysts. Rather ironically, oped technology the NEXUS® catalyst RE metals are not so rare. However, family was commercialized in 1997, as INDUSTRY NEWS they tend to be concentrated in hard- a RE-free catalyst family for low-metal Cameroon on Track to Modernize its to-extract ore deposits. As a result, the feed applications. NEXUS® catalyst has 30-yr Old Refinery world’s supply comes from only a few since been used in 10 applications.2-3 China’s two Largest Refiners Raising sources. China alone accounts for 95% In 2008, a refiner conducted back- Crude Processing Capacity of the world’s RE metal output. Recent to-back catalyst evaluations comparing export quota restrictions on RE met- NEXUS® catalyst to a competitive RE- Sinopec Takes 37.5% Stake in Saudi als from China have caused the price of based FCC catalyst. Feed properties and Aramco Yanbu Project these metals to rapidly rise, accelerating operating parameters for both periods Sinopec and KPC Refinery Startup * development of RE-free FCC catalysts. were similar. The E-cat gas and hydro- Planned for 2013 Grace has a successful history of gen factors during the back-to-back test- Shell Sells Stanlow Refinery to India’s developing innovative FCC catalysts, ing showed how NEXUS® catalyst is Essar Energy including RE metals catalysts.1 Grace more selective at constant nickel equiva- later developed RE-free FCC catalysts lents than the competitive offering. Sohar Refinery Expanding Capacity to and zeolite components that enhanced FCC product yields obtained during 187,000 bpd gasoline octane in the 1980s and 1990s back-to-back testing are shown in Table BP Whiting Modernization Deferred until delivering activity and stability without 1. NEXUS® catalyst is more selective Mid-2013 using RE metals. Over 85% of Grace at constant nickel equivalents than the Total Adding New GO Hydrotreater at catalysts used at the time consisted of competitive offering. NEXUS® cata- Gonfreville Refinery RE-free zeolites. Later in the 1990s, lyst provided higher Cont. page 2 Jurong Refinery Diesel Hydrotreater Startup Expected in 2014 Table 1. FCC Product Yields Comparing NEXUS® PDVSA Project Includes 85,000 bpd Catalyst with a Competitor’s Rare-Earth Based Catalyst. Hydrotreater Product Yields NEXUS®-346 Competitor Delta TNK-BP Investments Include Increasing H2 0.03 0.07 -0.04 Hydrotreating and Hydrocracking Capacity China Sets Limits on Rare Earth Output Dry Gas (H2S) 3.6 4.12 -0.52 Grace - Chevron Joint Venture Celebrates LPG 16.25 18.19 -1.94 Tenth Anniversary Gasoline C5-210°C 50.16 45.2 4.96 LCO 210-360°C 15.62 18.72 -3.1 EDITORIALLY SPEAKING Crude Costs and Higher Operating MCB 360+ °C 7.98 7.68 0.3 Expenses Cut Into Refinery Profits Coke 4.72 4.56 0.16 CALENDAR Conversion 76.39 73.6 2.79 Copyright 2011. Refinery Operations RefineryOperations.com | 2011.04.06 1 April 06, 2011 conversion (2.8 wt%), lower hydro- gen yield (0.04 wt%), a lower dry gas Table 2. ACE Pilot Plant Testing Comparing yield (0.5 wt%) and a higher gasoline REesolution™ Catalyst with NEXUS® Catalyst. yield (5.0 wt%). To summarize, the ACE Yields at Constant Conversion (CPS-3 deactivation, metals-free) refiner considered the NEXUS® cat- alyst trial to be a complete success, NEXUS® Catalyst REsolution™ Catalyst realizing a benefit of approximately Cat-to-oil 4.9 4.5 1.0 million Euros per year, remaining LPG olefins, wt% 13.7 14.2 on NEXUS® catalyst to this day. Gasoline, wt% 49.4 49.4 Low Metal Feed Applications HCO, wt% 10 9.8 Combining the RE-free Z-21 with Coke, wt% 2.3 2.2 new matrices has resulted in the new families of REsolution™ catalysts and REBEL™ catalysts. RE-free Table 3. REBEL™ Catalyst Delivers the Same Activity REsolution™ catalysts are intended and Selectivity Over Resid Feedstock. for low metal feed applications, and represent a further improvement on ACE Yields at Constant Conversion (CPS-3 deactivation, 3000 ppm Ni + V) NEXUS® catalyst performance. REBEL™ Catalyst MIDAS®-100 Within each family of REsolution™ catalysts, the ability to indepen- Cat-to-oil 5.8 5.5 dently adjust activity and selectivi- Dry Gas, wt% 1.8 1.8 ties of zeolite and matrix, as well Propylene, wt% 3.5 3.5 as the ratio of zeolite/matrix activ- ity allow for a tremendous degree of Butylenes, wt% 5.2 5.4 formulation flexibility. Gasoline, wt% 46.6 46.8 For low metal applications REs- olution™ will match/improve the Bottoms, wt% 9.6 9.5 performance of standard RE-based Coke, wt% 4.2 4.3 catalysts. Table 2 shows ACE pilot plant testing (CPS-3 deactiva- tion, no metals) comparing REso- Table 4. Z-22 Delivers the Same Equivalent Activity and lution™ and NEXUS catalysts. It Selectivity Without Rare Earth. can be seen that REsolution™ pro- ACE Yields at Constant Conversion vides higher conversion and LPG olefins yield, as well as similar Z-22 REUSY gasoline yield, bottoms upgrading Cat-to-oil 6.6 6.8 and coke. Several trials of REsolu- tion™ catalysts are currently taking Dry Gas, wt% 1.5 1.4 place in Europe. Propylene, wt% 4.6 4.3 Further R&D work has provided a Butylenes, wt% 11 10.4 new RE-free high matrix catalyst sys- tem for FCC applications. REBEL™ Gasoline, wt% 52 53 catalyst, formulated with Z-21, dem- Bottoms, wt% 6.7 6.8 onstrates similar activity and selec- Coke, wt% 2.3 2.2 tivity as Midas 100® catalyst, and is now under development (Table 3). Most recently, a breakthrough Z-22 zeolite has been success- REactoR™ catalyst utilizes the Z-22 proprietary stabilization process has fully produced. Several new catalyst zeolite, but also incorporates the been achieved in combination with a families utilizing Z-22 are now being processing technologies used in NA- unique treatment step to boost acid- introduced for hydrotreated or low- DIUS™ catalyst (an RE-based cata- ity, resulting in the RE-free Z-22 to-moderate feed-metal applications, lyst for low-metal feed applications). zeolite. Relative to REUSY, Z-22 with one commercial trial currently ACE pilot plant testing (CPS-3 de- provides equivalent activity, higher underway in North America. activation, metals free) demonstrates LPG olefins and gasoline octane, at Introduction of RE-free catalysts that both catalysts show similar selec- constant bottoms and coke make, as utilizing the Z-22 zeolite is also being tivities in terms of dry gas, coke and shown in Table 4. planned in Europe. For example, bottoms upgrading, Cont. page 3 Copyright 2011. Refinery Operations RefineryOperations.com | 2011.04.06 2 April 06, 2011 whilst REactoR™ catalyst provides Table 5. ACE Testing Comparing NADIUS™ with higher yields of LPG olefins at the ex- pense of some gasoline yield (Table 5). ReactoR™ Catalyst. REplaceR™ catalyst is another new CPS-3 Deactivation, Metals-Free RE-free catalyst family that is based on NADIUS™ Catalyst Reactor™ Catalyst the Z-22 zeolite, but this catalyst incor- porates the processing technologies used Conversion, wt% 75 75 in NaceR™ catalyst (another RE-based LPG Olefins, wt% 14.6 15.3 catalyst for low-metal feed applications). ACE pilot plant testing (CPS-3 deactiva- Gasoline, wt% 51 50.3 tion, metals free) comparing REplaceR™ Bottoms, wt% 10.3 10.3 with NaceR™ show that REplaceR™ Coke, wt% 1.7 1.6 provides similarly high activity, slightly higher LPG olefin yields and similar bottoms upgrading and coke yield. Table 6. ACE Testing Comparing NEKTOR™ Catalyst These ACE pilot plant results dem- with NEKTOR™/ReduceR™ Catalysts (70/30). onstrate that for low-metal applications ACE Yields at Constant Conversion (CPS-3 deactivation, 2500/4500 ppm V/Ni) REactoR™ and REplaceR™ catalyst are suitable RE-free alternatives to es- NEKTOR™ Catalyst 70% NEKTOR™/30% tablished rare-earth based catalysts. ReduceR™ Within these catalyst families the matrix Cat-to-oil 4.5 5.3 type as well as the zeolite/matrix ratio LPG olefins, wt% 13.8 13.9 can be varied. Additional formulation flexibility is possible, enabling fine tun- Gasoline, wt% 51 50.9 ing of the catalyst to suit FCCU-specific Bottoms, wt% 7.2 7 requirements regarding activity and se- lectivity. REactoR™ and REplaceR™ Coke, wt% 5.5 5.3 catalysts are also manufactured with the REduceR™ catalyst are shown in Table • REactoR™ catalyst: Contains the proprietary Grace Davison alumina-sol 6. To summarize, REduceR™ catalyst, newly developed RE-free Z-22 binder system, which ensures low par- a RE-free resid catalyst can be blended zeolite with the application of the ticulate emissions due to its excellent with a RE-based resid catalyst to pro- processing technologies used in attrition resistance. vide similar performance in the key NADIUS™ catalyst areas of activity, bottoms upgrading and • REplaceR™ catalyst: Contains RE-Free Catalyst for Resid coke yield. Grace is continuing R&D the newly developed RE-free Z-22 Feed Applications work to develop a RE-free catalyst with zeolite with the application of the Due to the additional demands placed the stability and performance to allow processing technologies used in on zeolite stability, the development the complete elimination of RE-based NaceR™ of RE-free catalysts for the resid feed grades in resid applications.
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