Hydrothermal Technology for recovery of Molybdenum from spent Hydro-Treating catalysts. Wilfred van Wijk Rob van der Meij December 3, 2014

Rob van der Meij Wilfred van Wijk Serial Entrepreneur in Clean Tech > 25 years in catalyst, water and chemical industry Akzo Nobel, Cap Gemini, Shell Chemicals 7 years Start Ups Catalysts, Biofuels, Water, Separations KiOR, fluXXion, BiAqua, Hermes Catalysts, HyVent Chemical Engineer TU Delft, NL Wilfred van Wijk > 20 years in Organophosphorus, Specialty monomer, Organics, Chemical by-and waste streams and general chemical industry CYTEC Industries Phosphine and derivatives 5 years providing chemistry, chemical and technology solutions; HyVent, Gulf Interchem, ICSP. Chemist, University of Leiden, NL December 3, 2014

Processes in the sub- or super- critical regime of water HyVent Technology Core Technology ⇨ HydroThermal treatment Testing facilities in The Netherlands and Germany Processes in the sub- or super- critical regime of water December 3, 2014

HyVent Technology application areas Synthesis Oxides Ferrites Heavy Oil Upgrading Bitumen Vacuum Resid Removal of metals Spent refinery catalysts Mixed oxides Destruction Toxic wastes Organic/Inorganic mixtures High COD water December 3, 2014

Historical Molybdenum (Mo) pricing Hydroprocessing Catalyst contain 15-25% MoO3 MoO3 price (USD/lb) ? Historical pricing 2.5 $/lb Year December 3, 2014

Spent hydrotreating catalysts are both a hassle and a source of value for refiners 160,000 tpa Remove S from oil Legal waste disposal obligation Hazardous waste >20% metals Largely Mo 20 % Carbon and Sulfur Liability risk when done incorrectly Needs to be removed prior to processing Co-Mo Ni-Mo Export Documentation and transport hassle Needs to be removed prior to processing Metals value 4000 $/ton December 3, 2014

High costs in metal recovery value chain limits return to refiner Unload spent catalyst Special packaging Roaster for C,S removal Metal reclaim > 65% generated in North America, Europe, Middle East > 65% reclaim capacity in Asia ⇨ Large transport volumes, Export chemical waste Large facilities Roasting and metal reclaim often not at same site ⇨ Multi-step location, international processing, documentation hassle Total costs > $ 2500 /ton December 3, 2014

Current metal recovery technologies for Mo and V have serious limitations Roasting for Carbon and Sulfur removal Environmentally unfriendly High capital investment, High maintenance Pyro metal recovery Smelting of material in electronic furnaces yielding Ferro-alloys used in steel industry, no re-use for catalysts Low recovery value (alloy) High capital investment, High energy consumption Hydrometallurgical metal recovery Chemical leaching with acid or base materials Complex processing with many contamination limitations Environmentally unfriendly waste waters December 3, 2014

HyVent’s Integrated Processing Scheme Hydrothermal processing Metal Recovery Spent Catalysts Water energy CO2, N2 Metal salts solids Integrated Metal Recovery Process Hydrothermal dissolution of C, S and metals Destruction of organic compounds Combination of proven processes from catalyst and battery recycle industry Zero Liquid Discharge process High recovery value for M and V December 3, 2014

The HyVent process is environmentally friendly No waste water or NOX and SOX emissions Pretreatment Reactor Separation Recovery Spent Catalyst V- recovery Vanadium salt feed depressurize Mo recovery Molybdenum salt HT Reactor treatment + leaching Water grind Liquids liquids Clean water for re-use Water treatment centrifuge mill Salts for disposal Solids Additives mix Solids collection Alumina/Ni/Co cake HP Pump December 3, 2014

HyVent uses all commercially proven equipment Tubular Hydrothermal Reactor system All stackable, modular container framed & sized equipment Slurry of un-regenerated catalyst prior to hydrothermal treatment December 3, 2014

HyVent’s process has strong advantages Current Processes Large, fixed units High CAPEX Multi-location process: - Roasting separate from metal recovery - multi transport, non-local - export Metal recovery pyrometallugy ⇨ ferro-alloy (low value) hydrometallurgy ⇨ large acqueous waste volumes Gas emissions Sulfuroxides, CO2, NOx and C-compounds HyVent Hydrothermal Process Modular, small Low CAPEX Local, single location process ⇨ C & S removal in process ⇨ Local single transport Mo and V compound as salt solutions ⇨ high value Zero Liquid Discharge ⇨ recycle process water December 3, 2014

HyVent will build local, customized, modular facilities to eliminate transport hassle and reduce costs Modular, containerized local facility NO transport, NO documentation hassle High return value for Mo and V metal recovery Modular facility with ‘plug and play’ construction set up Low CAPEX ⇨ 5-6 million USD per plant ZLD processing, full water recycle, no emissions High flexibility to adapt to local market Mo or Mo and V recovery Chemical catalyst processing with other metals (Cu, Zn, RE etc.) add on possible Noble metal recovery scheme under development December 3, 2014

Global hydro-processing spent catalyst generation (tons/year) Several 1000-4000 tpa facilities can be build around refining centers in the world 2 2 2 Asia 3 2 3 2 1 1 2 1 1 Americas Europe Global hydro-processing spent catalyst generation (tons/year) Potential number of facilities by region # America’s, Europe, export >65 % of spent catalyst to Asia Pacific now (VN, K, CN, TW)

Net return difference for refinery HyVent vs competition Better return to refiner with HyVent: ⇨ avg >700 $/ton over past 15 years !! Net return difference for refinery HyVent vs competition (current pricing) USD / ton Year (+2000) December 3, 2014

Higher value return to Refinery without hassle Recovery of Mo reduces refinery exposure to metal price fluctuations Swap recovered Mo with fresh catalyst Mo Better value recovery for refinery No documentation and transport hassle for refinery No export waste liability risk Long term guaranteed off-take agreement December 3, 2014

Thank you for your attention Closing remarks The HyVent integrated HydroThermal process for treatment of spent refinery catalyst and recovery of Molybdenum offers an environmentally friendly, economic and flexible processing technology in answer to changing market demand and requirements Thank you for your attention December 3, 2014