Albemarle Catalysts: Refining and Chemical Catalyst Developments of the Past, Present and Future Case studies on the interface of petroleum refining and (petro)chemicals for open market and custom needs Ludo Boot Technical Sales Manager – Albemarle Catalysts Company BV - NL Niraj Ashar, Ganesh Prakasham Middle East and India Sales, Albemarle Middle East (FZE) - UAE Aaron Williams Worldwide Business Director – Albemarle Corporation – Chemical Catalysts Introduction to Albemarle Refining Lithium and Bromine Chemetall® Solutions Advanced Materials Specialties Surface Treatment • FCC for Resid • Li Metals (Batt) • Flame retardants for • Aerospace polyolefins, elastomers, • FCC for Max Propylene • Li Foils, Components • Aluminum finishing engineering plastics, • FCC for VGO • Li Salts (Batt) styrenics, thermosets, • Appliances, HVAC • Hydroprocessing • Curatives insulation foams & • Automotive OEM textiles • Isomerization • Organometallics • Glass processing • Oil Field Products • Alkylation • Polymer Catalysts and Components • Hg Control • Chemical Catalysts Organizational structure effective January 1, 2016 2 Global Footprint is a Competitive Advantage Global Headquarters Manufacturing Manufacturing/Sales/R&D Sales/Administrative Integrated Business Operations R&D Albemarle employs approximately 6,900 people and serves customers in approximately 100 countries 3 … when dealing with a global customer base Refinery Scheme Refinery Scheme: Albemarle’s Presence Refining Solutions Heavy Oil Upgrading Clean Fuels Technologies Heavy Oil Upgrading Clean Fuels Technologies • FCC for Resid • Hydroprocessing • FCC for Max Propylene • Isomerization • FCC for Vacuum Gas Oil (VGO) • Alkylation • Solid Phosphoric Acid (SPA) Catalysts • Technology Licensing • Chemical Catalysts 7 Refining Solutions Fluid Catalytic Cracking Hydroprocessing Clean Fuels Technologies • Decades of experience • Decades of experience, technical support • Market leader in Max C3= • Market leader in distillates • Spray-dried zeolite • Fixed bed catalyst catalyst SULFUR- HYDROGEN CONTAINING FEED Zone 1 FIXED BED REACTOR Zone 2 Zone 3 DESULPHURIZED PRODUCTS (e.g., 10 ppm S ULSD) + H2S 8 Refining Solutions Heavy Oil Upgrading Clean Fuels Technologies Heavy Oil Upgrading Clean Fuels Technologies • FCC for Resid • Hydroprocessing • FCC for Max Propylene • Isomerization • FCC for Vacuum Gas Oil (VGO) • Alkylation • Solid Phosphoric Acid (SPA) Catalysts • Technology Licensing •Chemical Catalysts 9 Chemical Catalysts • Part of Refining Solutions global business unit (GBU) • Mix of catalyst products and developments closer to the refinery and in the middle of (petro-) chemical complex Oxychlorination Methylamines Specialty New Catalyst Custom Catalysts Catalyst Zeolites Businesses Catalysts •EDC • Methylamines • Building on zeolites • Purification • Various applications production production expertise and adsorbents • Scale-up of lab • Catalyst leader for • Global catalyst manufacturing • Refining recipes Mitsui technology leader for Davy capacity/capability • Petrochemical • Commercial • Established technology • Own developments • Synthesis gas production of pilot and customer catalyst provider • Evaluating other • Gas processing scale recipes for amines applications (acid • Synthesis gas • Cooperation with OxyVinyls/Vinnolit technologies catalysis, end users or • Portfolio of technology absorption) licensors catalysts Refinery Scheme Petrochemicals Scheme Petrochemicals Scheme Albemarle Chemical Catalysts Research and development skills Chemicals handling capabilities Custom catalysts Processing competencies Jointly developed products Open market grades • Oxychlorination • Methylamines • Zeolites •… Albemarle Chemical Catalysts Capabilities – Unit Operations Albemarle Catalysts capabilities HOU CFT ChemCat Gel chemistry 99 9 Specialty Zeolites 99 9 Washing/Separation 99 9 Ion Exchange 99 9 Drying/Calcination 99 9 Particle Sizing 99 9 Metals Impregnation 99 9 Powder Handling 99 9 Process Optimization 99 9 HTE testing 99 9 Pelletizing 99 Extruding 99 Spray Drying 99 9 Quality Control 99 9 Packaging 99 9 Past, Present and Future • Capabilities enabled developments across the entire range of Refinery and Petrochemical applications » Current open market grades for oxychlorination and methylamines, for example, started as custom developments » Zeolite development and production capabilities originally in FCC were expanded to separate product line and custom catalyst components • Cases in the interface area of Refining and Petrochemicals » Present: Fast development of ATX catalyst » Past, Present and Future: Solid Acid Alkylation » Future: Mixed Alcohols Catalyst MA-15 Case 1: ATX-720 • ATX series: various oxidic supports and catalysts, including zeolite components for activity • Introduction of a novel zeolite-based product called ATX™-720. Product was tailored and scaled up by our research, development and technology department in Amsterdam, the Netherlands Tested and approved by a US customer for a catalytic absorption application Ideation Proof of Concept Research Development Commercialization Understanding Commercial Customer Small Scale Pilot Scale Small Scale Scale Challenges Case 1: ATX-720 • Project all started with a simple request from a new customer for a high-silica ultra-stable Y-type ACZeo zeolite sample Zeolite Type ACZeo-Y307 ACZeo-Y411 ACZeo-Y530 ACZeo-Y655 ACZeo-Y756 Application Catalysis Catalysis Catalysis Catalysis Catalysis Adsorption Adsorption Adsorption Adsorption Adsorption XRD Crystallinity 95+ % 95+ % 90+ % 90+ % 90+ % Cation H or NH4 HHHH SiO2/Al2O3-Ratio 7.511305555 • Customer also needed to outsource product manufacturing » In a short time, moved from grams to metric tons of a novel zeolite product with unique performance and within the required specifications » Satisfied customer, thanks to Albemarle’s technical expertise and the engagement and efforts of all functions involved in the process for manufacturing this customized zeolite product Ideation Proof of Concept Research Development Commercialization Understanding Commercial Customer Small Scale Pilot Scale Small Scale Scale Challenges Case 2: Alkylation • Phases in the project the same » Starts with an idea » Ends with commercialization • “Different” scale from previous case » Timescale » Investment scale » Scale of impact on refinery/petrochemical i-C4 + olefin (C4 or mixed) Æ alkylate (i-octane) Ideation Proof of Concept Research Development Commercialization Understanding Commercial Customer Small Scale Pilot Scale Small Scale Scale Challenges Case 2: Alkylation • Process scheme developed in cooperation with partners Case 2: Alkylation • Built on Albemarle’s AlkyStar™ noble metal on zeolite catalyst • Process and catalyst cannot be developed independently • Result: Commercial unit CB&I (Lummus Technology) provided license to Shandong Wonfull Petrochemical Group Co Process engineering design and construction for a first-of-a-kind solid- acid alkylation unit located in Shandong Province, China The unit will be capable of producing 100,000 ton/yr of alkylate Case 3: Mixed alcohols catalyst MA-15 • Commercial interest- where there is production of syngas » Feedstock indifferent • Synthesis of mixed alcohols occurs in a single reactor and the overall stoichiometry is: n CO + 2n H2 Æ CnH(2n + 1)OH + (n – 1) H2O • Methanol synthesis (n=1) CO + 2 H2 Æ CH3OH • Ethanol synthesis (n=2) CO + 2 H2 + CH3OH Æ C2H5OH + H2O • Propanol synthesis (n=3) CO + 2 H2 + C2H5OH Æ C3H7OH + H2O • Water gas shift reaction CO + H2O Æ CO2 + H2 Case 3: Mixed alcohols catalyst MA-15 • Dow Chemical demonstrated in the ‘80s that a CoMo catalyst was effective at converting syngas to mixed alcohols • Albemarle developed a process to produce an agglomerated CoMo catalyst in the oxidic form » A new production route was developed » Albemarle has the ability to scale-up the production to 100s of tons » The catalyst can be sulfided in-situ or ex-situ • Albemarle’s MA-15 catalyst » Does not need sulfur-free feed – in fact, ~100 ppm sulfur required to maintain activity » Can run ‘raw’ biosyngas » Robust with high activity and selectivity towards ethanol » Scalable – already at plant scale Case 3: Mixed Alcohols Catalyst MA-15 • Opportunities when either syngas is available and feed is monetized (biobased, coal, stranded gas) or when ethanol is in demand (gasoline additive) • Albemarle works with end users or process licensors to further develop the catalyst and process Ideation Proof of Concept Research Development Commercialization Understanding Commercial Customer Small Scale Pilot Scale Small Scale Scale Challenges Acknowledgements Albemarle R&D and Technology groups 1 • Amsterdam, Bayport and Baton Rouge R&D Centers 2 Partners and customers 3 Conference Organization Thanks! 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