![• New family of stabilized titania has been introduced to the market
• Technology is highly effective for improving thermal stability
• Optimal SCR activity and activity retention can be achieved
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SurfaceArea[m2/g]
Temperature [C]
New Stabilized Titania- Surface Area Stability
10 wt% Silica
Standard Technology
New Technology
Calcined 6 h in air Hydrothermally aged 16 h
100% Anatase
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DeNOxConversion,350C Ti-Si (10% SiO2) DT-58 DT-S10
Activity of Aged Catalysts
Nominal 10% SiO2, 10% WO3, 2%V2O5
Aged 800C, 16 h, 10% H2O
Latest Developments
…to meet the most stringent DeNOx catalyst requirements
Cristal patented technology allows
for better thermal stability and better NOx conversion
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Cristal_TiO2_World_Summit_Presentation FINAL Oct 12
- 1. BEYOND PIGMENT: The Growing Benefits of Titanium Dioxide for Our Society Jean-François Pasquier Business Director Specialty Chemicals & Materials jean-francois.pasquier@cristal.com TiO2 World Summit Cleveland October 2016
- 2. TiO2 Beyond Pigment: Ultrafine and Other Specialties The Demonstrated Benefits of Ultrafine TiO2 in Catalysts New Opportunities to Meet Current and Future Society Challenges Agenda 2
- 3. • Extensively studied • Oxide support with transition metal chemistry • Photoactive • Established methods for structured materials • Tailored properties related to manufacturing route • Established manufacturing routes for economies of scale TiO2 (001) (011) (101) (a) (101) (011) A material for innovation 3
- 4. • Well established manufacturing processes giving economies of scale • Versatile physical and chemical properties related to the technology • Numerous modes of introduction into the catalyst or material system, i.e. powders, gels, sols, chemicals Cristal Ultrafine TiO2 Technologies Pigmentary TiO2 Anatase and Rutile 200 - 300 nm, refractive index Optimized for light scattering properties and dispersion < 100 nm, surface reactivity & semi-conductor properties Ultrafine products from different technologies Opening a large spectrum of opportunities 4
- 5. Global technology leader in titania-based applications Major applications include: • Emissions Control • Refining Catalysis • Petrochemical Catalysis • Energy Storage • Photovoltaics • Photocatalysis • Colored Pigments • Electronics • Ceramics Over 30 years of industry-leading experience in ultrafine TiO2 for specialty applications 5
- 6. DeNOx (stationary) DeNOx (mobile) DeNOx (off-road) Oxidation Mobile Oxidation NO, HC, CO, PM DeNOx (marine) NOx reduction into N2 (with ammonia/urea) TiO2-based Products for Environmental Catalysis TiO2 A key component of environmental applications 6
- 7. 0 20 000 000 40 000 000 60 000 000 80 000 000 100 000 000 120 000 000 Cumulative NOx conversion in mt Ultrafine TiO2 Contribution to Depollution Cristal Estimate Based on Publically Available Information More than 110 million MT NOx converted in power plants in the last 35 years 7
- 8. Physical Properties • Crystallinity • Porosity • Thermal Stability Chemistry • Active Phase • Mixed Oxides • Acidity Catalysis • DeNOx • Petrochem • Photocat TiO2 A material of choice for innovation in catalysis Manufacturing • Process • Delivery Systems • Rheology 8
- 9. Thermal stability • Euro VI and US 2010 – SCR + DPF needed • 600°C thermal stability generally far enough with passive regeneration of the DPF • More thermal stability is needed with active regeneration • The SCRF technology (SCR on DPF) requires significant thermal stability Cristal emphasis on improving both Activity at low temperature • Regulatory trends towards low NOx • Necessity to comply with fuel economy requirements and CO2 emissions limit • Thermal efficiency results in lower exhaust temperature The challenges of China VI regulation Latest Developments …to meet the most stringent DeNOx catalyst requirements 9
- 10. • New family of stabilized titania has been introduced to the market • Technology is highly effective for improving thermal stability • Optimal SCR activity and activity retention can be achieved 0 50 100 150 200 250 300 500 550 600 650 700 750 800 850 900 950 SurfaceArea[m2/g] Temperature [C] New Stabilized Titania- Surface Area Stability 10 wt% Silica Standard Technology New Technology Calcined 6 h in air Hydrothermally aged 16 h 100% Anatase 0 10 20 30 40 50 60 70 DeNOxConversion,350C Ti-Si (10% SiO2) DT-58 DT-S10 Activity of Aged Catalysts Nominal 10% SiO2, 10% WO3, 2%V2O5 Aged 800C, 16 h, 10% H2O Latest Developments …to meet the most stringent DeNOx catalyst requirements Cristal patented technology allows for better thermal stability and better NOx conversion 10
- 11. Alumina Supported Cristal TiO2 Supported US 8,168,562; S.M. Augustine US 6,022,823; S.M. Augustine, D.W. Smith, R.M. Hanes, M.D. Evans Cristal TiO2 improves stability of PdAu catalysts 11 Demonstrated Performance of TiO2 for Petrochem Catalysts Vinyl Acetate Process – Optimum Metal-Support Interaction Performance of VAM Catalysts Performance of Allyl Acetate Catalysts
- 12. New Opportunities to Meet Current Society Challenges Environment: Photocatalysis for Self- Cleaning and Air Depollution Water Conservation: TiO2 Uses for Water Treatment Energy: TiO2 for Power Generation and Power Storage 12
- 13. • The ultrafine TiO2 can be incorporated into the product (i.e. paint, concrete, etc.) or post applied to the surface (i.e. sol post treatment) • There are two mechanisms of ultrafine TiO2 that create the self-cleaning functionality: – Hydrophilicity of the surface – Degradation of organic contaminants Initial Application Performance after 19 months How does ultrafine TiO2 impact self cleaning? CristalACTiV™ Ultrafine TiO2 Photocatalytic Properties for Self Cleaning Utilizing ultrafine TiO2 to create self-cleaning surfaces 13
- 14. CristalACTiV™ Ultrafine TiO2 Effectiveness for Depollution Key Learnings • Technology shift — cement to paint to sol technology • Trial success correlates to activity of the system • Application area is a key factor — Camden/Sir John Cass Trial • Measurement system failures — Sir John Cass, High Holborn • Measured response is only possible if pollution source is significant- Konningstunnel Field trial evolution and learnings Picada High Holborn Milan Tunnel Photopaq Vinci Car Park Sir John Cass School Manilla Trial Koningstunnel Yanbu Housing Camden 0 1 2 3 4 5 6 7 8 9 10 1995 2000 2005 2010 2015 2020 Progression (Years) Cristal Field Studies Cement-based technology Paint Sol technology Performance 14
- 15. Active Layer 0 5 10 15 20 Past Technology Intermediate Technology New Technology Substrate Substrate PC in Cement Paint - Dispersion of PC Sol-based Treatment Technology DispersionPowder Sol Application >3 micron; 10% PC effective >10 micron; 4%PC effective <1 micron; 100% PC effective Surface Area 80-50 m2/g10-50 m2/g 350+ m2/g Technology Improvement Active Layer Old Technology Comments Needs activationCan be deactivated Instantaneous CristalACTiV™ Ultrafine TiO2 Effectiveness for Depollution Technology evolution Photocatalytic Capabilities of Test Materials NOx Removal (g/month/m2) 15
- 16. Assumptions • The typical Euro VI diesel car emits 80 mg/km of NOx pollutants • Avg. driver in the UK drives 12,700km per year • Total pollution approximately 1,000 grams of NOx per vehicle per annum Solutions • A typical forest canopy can remove 1.64 grams of NOx per square meter per annum • CristalACTiV photocat application – removes 0.5 grams of NOx per square meter per day (182.5 grams per year), at a cost of £3/m2 • Other options – traffic control, tolls to enter clean air zones, conversion to cleaner fuels/electric cars – Iintrusive to people/longer- term solutions to develop Cristal Estimate Based on Publically Available Information http://www.fs.fed.us/ne/newtown_square/publications/ other_publishers/OCR/ne_2006_nowak001.pdf 0 100 200 300 400 500 600 700 0 20 40 60 80 100 120 140 160 180 200 Tree Canopy Photocatalytic TiO2 Area(inm2) NOxPollutantReduction(ing/m2) NOx Emission Reduction of a Single Car Choice of Trees or Photocatalytic TiO2 to Treat Emissions NOx Removed per sq. meter No. of sq. meters required to treat emissions from 1 car Treatment Area = 5.5 m2 Treatment Cost = $22 Treatment area= 610 m2 CristalACTiV™ Ultrafine TiO2 Effectiveness for Depollution Costs to remove pollution 16
- 17. Ultrafine TiO2 Offers New Options for Water Filtration • Access to safe, pure drinking water is becoming a growing societal concern • Traditional water treatment techniques include: o flocculation and filtration methods for solids removal o chemical disinfection for purification against microorganisms • Treatment systems can occur at the source, by the municipalities, or at point of use What role does ultrafine TiO2 have in water treatments? Filtration – The micropore structure of UF TiO2 can be used to remove harmful contaminants Disinfection – The reaction mechanism of UF TiO2 and UV light can be used for redox reaction to treat organic pollutants 17
- 18. PSCLiquid DSC Solid Hole Transport Material Titania Perovskite Light Absorber Liquid Electrolyte Titania Dye Nano-Platinum Catalyst Si Solar CellHuman Hair 500 nanometres TiO2: A Key Element for the Solar Cells Next Generation Novel Architecture of PSC 18 Source: DYESOL Limited
- 19. TiO2 in Batteries: Lithium Titanate Oxide • Lithium Titanate Oxide (LTO) replaces the graphite as anode material • LTO is compatible with all cathode materials, but is generally used in combination with manganese-based materials. • Highest safety of Li-Ion technologies • Quick recharge rates • High cycle life- charge/discharge (>5,000 discharges cycles vs. ~400 of a regular Li-ion) • Good performance at low temperature • LTO battery’s can be shipped and stored at zero charge • Can use aluminum as a battery case – lightweight LTOBattery Characteristics 19
- 20. Samples of LTO material have been produced from the HPX products in the Cristal labs Tested for discharge capacity Patented technology LTO produced from HPX-100 LTO produced from HPX-400 TiO2 in batteries: Lithium Titanate Oxide LTO manufactured using Cristal TiO2 as precursor 20
- 21. HPX-400 • 1C = cell full discharged in 1 hour • C/5 = cell fully discharged in 5 hours • 10/C = cell fully discharged in 6 minutes • Higher capacity at a given discharge rate is preferred • Test performed by a Cristal partner • Test at 80% loading • Discharge capacities vs. charge/ discharge cycles HPX-100 TiO2 in batteries: Lithium Titanate Oxide LTO manufactured using Cristal TiO2 as precursor LTO manufactured from Cristal products demonstrates higher discharge stability! 21
- 22. Beyond Pigment… • TiO2, and more specifically Ultrafine TiO2, has demonstrated its ability to dramatically improve the quality of life and to meet growing societal challenges • New environmental applications are emerging and novel TiO2 materials for water conservation and for energy generation and storage are being developed • Cristal offers the largest range of Specialty TiO2 and a robust experience to meet the existing and coming challenges 22
- 23. Thank you!