We create chemistry that makes individual refiners love fueling the world. Advances in FCC Catalyst Technology and Services Jeremy Mayol, Vasilis Komvokis, and Carl Keeley 11th May, 2015 19.12.2014 INTERN 1 Agenda 1. Resid FCC Catalyst 2. ZSM-5 Additive for Propylene Resid to Propylene 3. Technical Services R R to P 2 P FCC Catalyst 3 Nickel Dehydrogenation activity leading to increased H2 and coke ACE H2/C1 Ratio Benchmark: Impact of Contaminant Metals on FCC Unit Operation 6 5 4 3 2 1 0 0 Catalyst deactivation, with some dehydrogenation activity 5,000 6,000 80 75 70 65 60 0 4 2,000 3,000 4,000 Nickel, ppm 85 FACT, wt% Vanadium 1,000 5,000 10,000 V+Na, ppm 15,000 R&D: Analysis of Resid FCC Catalyst Electron micro-probing Scanning Electron Microscopy (SEM) Nickel Vanadium is located throughout particle Nickel is concentrated in the outer-layer of catalyst (5-10 micron) 5 Innovation: Breakthrough Multi-stage Reaction Catalyst (MSRC) Can we improve upon the DMS based Flex-Tec by distributing the specialty alumina where nickel is predominantly located? Alumina Flex-Tec Fortress Catalyst Yes: By using a technology with increased alumina content in the outer-stage MSRC combines two or more FCC catalyst functionalities within a single catalyst particle 6 Case Study: Innovative Resid Cracking Catalysts Improve R2R Unit Profitability Tamoil’s Collombey refinery: R2R FCC Unit with 100% atmospheric residue feed CCR up to 7 wt% and Ni+V up to 10,000 ppm Two trials: Aegis: Outperformed the resid catalyst with the largest market share in EMEA. Improved LPG selectivity, outstanding benefit on bottoms cracking and improved conversion. Fortress: Further improved flexibility to upgrade heavy resid feedstock with increased metals content. Y.A. Jollien et al., Use an innovative cracking catalyst to upgrade residue feedstock, Hydrocarbon Processing, Feb 2013 Y.A. Jollien et al., Multi-Stage Reaction Catalyst with Advanced Metals Tolerance, PTQ Q4 2013 Case Study: Record Conversion at IsoCAR and Contaminant Metals Level +3-4% conversion increased, at iso-catalyst addition rate Y.A. Jollien et al., Multi-Stage Reaction Catalyst with Advanced Metals Tolerance, PTQ Q4 2013 8 Case Study: Record Bottoms Upgrading at Iso-Conversion Bottoms upgrading increased: increase in the LCO/slurry ratio, at higher conversion, was +12-15% Y.A. Jollien et al., Multi-Stage Reaction Catalyst with Advanced Metals Tolerance, PTQ Q4 2013 9 Case Study: Innovative Resid Cracking Catalysts Improve R2R Unit Profitability Aegis: Improved LPG selectivity, outstanding benefit on bottoms cracking and improved conversion. +0.40 $/bbl compared with resid catalyst with the largest market share in EMEA Fortress: Further improved flexibility to upgrade heavy resid feedstock with increased metals content. +0.30 $/bbl compared to lower contaminant metal operating period FCC Products + Technical Services = Success! Y.A. Jollien et al., Use an innovative cracking catalyst to upgrade residue feedstock, Hydrocarbon Processing, Feb 2013 Y.A. Jollien et al., Multi-Stage Reaction Catalyst with Advanced Metals Tolerance, PTQ Q4 2013 ZIP Olefins Additive 11 Resid to Propylene is a Combination of Technologies (Catalyst and Additive) FCC Catalyst RE-Y Zeolite Feed ZSM-5 Linear and near-linear C6-C9 olefins Pore Diameter of 7.4 Å C3 and C4 Olefins ↑ Gasoline Octane Pore Diameter of 5.1 to 5.6 Å 7.4 Å Higher ZSM-5 usage: Increases LPG yield, more light olefins are produced Gasoline yield declines, but its octane improves C. KEELEY, V. KOMVOKIS, M. MIRANDA, et. al., ZSM-5 Additive Maximises Propylene, PTQ Catalysis 2015 R&D: Diminishing Returns with Increasing ZSM-5 Loading 90% of incremental propylene from first 20% ZSM-5 *40% crystal Opportunity for improvement Partly limited by the availability of C6-C9 olefins Develop new ZSM-5 additive to increase propylene yield at the same zeolite content C. KEELEY, V. KOMVOKIS, M. MIRANDA, et. al., ZSM-5 Additive Maximises Propylene, PTQ Catalysis 2015 Innovation: ZIP Olefins Additive – Multi-stage Phosphorus treatment Phosphorus ZSM-5 Treatment Pretreated ZSM-5 Other Raws Phosphorus Source Binding Additional Zeolite stability Acid site strength/ Zeolite stability Spray dry Calcine Multi-stage phosphorus treatment to target all three functions C. KEELEY, V. KOMVOKIS, M. MIRANDA, et. al., ZSM-5 Additive Maximises Propylene, PTQ Catalysis 2015 Case Study: Maximum Propylene Solution Catalyst Commercial Trial Cepsa implemented advanced Max Propylene Solution (MPS Catalyst) based on MOA (ZSM-5 based additive) FCC increased propylene yield and processed higher amounts of heavy feed FCC profit increased by $2.50/bbl J.M. Llanes et al., New Catalyst Increase FCC olefin Yields, Hydrocarbon Processing, pgs. 63-66, April 2014 Case Study: Successful ZIP Olefins Additive Commercial Trial Propylene Yield (wt%) Model Developed on “Base” MOA Case Statistical model built to predict Propylene yield for a range of operating conditions MOA was replaced in the MPS catalyst with ZIP Actual propylene Estimated propylene 29-Jan Cepsa La Rábida decided to trial new ZIP Olefins Additive 26-Feb 26-Mar 23-Apr 21-May C. KEELEY, V. KOMVOKIS, M. MIRANDA, et. al., ZSM-5 Additive Maximises Propylene, PTQ Catalysis 2015 16 Case Study: Successful ZIP Olefins Additive Commercial Trial Propylene Yield (wt%) ZIP Trial Measured Against Model Predictions Similar Propylene for typical feed quality, using less additive This translates into a 20% reduction in additive consumption Actual propylene Estimated propylene 19-Apr 17-May 14-Jun 12-Jul 17 C. KEELEY, V. KOMVOKIS, M. MIRANDA, et. al., ZSM-5 Additive Maximises Propylene, PTQ Catalysis 2015 Case Study: Improved Flexibility to Process Heavier Feeds C. KEELEY, V. KOMVOKIS, M. MIRANDA, et. al., ZSM-5 Additive Maximises Propylene, PTQ Catalysis 2015 18 Benchmark: Propylene Source: BASF ECat benchmark database BASF Maximum Propylene Solution delivers highest Propylene yield 19 Technical Services 20 BASF is Committed to Being an Innovative Service Provider – Customer Success is our Goal Delivery of our product is just the beginning of our offerings BASF stands behind its products and through our technical service ensure our products perform and deliver value We work closely with each refinery in evaluating the FCC unit’s performance, operation limitations, and goals This relationship allows BASF to help our customers continuously optimize to meet their operating objectives Our team has a vast experience including process design, operational expertise, catalyst chemistry, economics, and troubleshooting 21 Innovation: Tools for Unit Optimization FCCU Modeling Benchmarking Gasoline Yield vs. Conversion Gasoline Yield, wt% 75 70 65 60 55 50 45 40 60 65 70 75 80 85 90 95 Conversion, wt% Pick up Factor is higher for new SOx reduction additive 800 Measured Statistical Model 700 Pick-up factor for improved SOx reduction additive can be calculated in real-time 600 Statistical Modeling 500 400 300 Base Case Start of new SOx reduction additive trial 200 Model= Function of feed S, flue gas O2, feed concarbon, feed rate, stripper steam rate and feed TBP dist. N.V. Karpov, C. Keeley, J. Mayol, et al., Case history: Optimization of FCCU with multivariate statistical modelling, Hydrocarbon Processing September 2013 22 New ECat Lab at hte GmbH in Germany – Quality Results with the Fastest Turnaround in the World! On December 2, 2014, BASF launched a new FCC catalyst testing and research laboratory at the hte GmbH (hte) site in Heidelberg, Germany hte is a wholly owned subsidiary of BASF SE and a leading provider of high throughput technology and services for enhancing research and development productivity Europe based laboratory significantly reduced ECat sample transit times, leading to faster service and also delivered a global flexibility by doubling BASF’s capability to enable the success of FCC units across all regions 80% of ECat results available within 20 hrs 100% of ECat results available within 30 hrs BASF Catalyst Management Services Operating experience Specialists handpicked from licensors, design companies and oil refineries Catalyst and additives Strong supplier to provide innovative solutions and technologies Technical Service Specialists for start-up, monitoring, troubleshooting, optimisation, training, etc. Logistic solution Strong supplier with global expertise able to provide a local solution Spent catalyst Strong supplier already working with cement companies, steel industry, etc. We are committed to Deliver Innovative Products to Improve FCC unit Profitability Multi-Stage Reaction Catalyst combines two or more FCC catalyst functionalities within a single catalyst particle The outer-stage of Fortress is enriched with specialty alumina to make it more effective at nickel passivation Fortress™ Resid FCC catalyst is commercially proven at eight refineries with similar results observed at all locations Novel ZIP Olefins Additive boosts Propylene production using less additive in CEPSA trial BASF Technical Service ensure our products perform and deliver value 25
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