Rajan K. Vempati, Ph.D. Prasad Rangaraju, Ph.D. Antonio Nanni Ph.D. Sridhar Komernini, Ph.D.

1. Biosilica from BiomassConstruction Material and EnergyChK Group, Inc. Plano, TexasACS National Meeting & ExpositionDallas, TXMarch 20, 2014 Rajan K. Vempati, Ph.D. Prasad Rangaraju, Ph.D. Antonio Nanni Ph.D. Sridhar Komernini, Ph.D. John Imhoff Subbaraman Viswanathan, Ph.D.

2. Project Goals • Manufacture Amorphous silica from biomass (Biosilica) with multiple uses • Construction material in High Strength Concrete • Additive in paints, plastics & tires • Zeolite manufacture • Sustainable Product • Unlike Other Food Products used in Bio-Fuels. The Rice Production for Human Consumption Unaffected. • Generate Revenues • From Biosilica - a high value product • Sell energy as steam and power • Create Jobs

3. Biosilica Renewable Cementitious Material • Rice Field (Upland Cultivation) Rice Hull From Rice Mills

4. Annual Capacities Competition Rice Mill From Area Biosilica Capacity Supply Silica Fumes (*) USA 10.5 Million Tons 0.4 Million Tons 60,000 Tons Worldwide 550 Million Tons 20 Million Tons -- (*) Silica fumes is a byproduct with limited capacity Supply of Rice Hulls • Agricultural Waste Generated from Rice Mills • Used as fuel for its caloric value. • Ash (black ash) with high carbon content is rejected as waste. • Off-white or white Biolica Supply Potential is high • Major competition – from silica fumes in Cement 4

5. Biosilica Premium Additive in High Performance Concrete (HPC)Value Chain for Biosilica Rice Cultivation and Processing in Rice Mills ChK Process Biosilica Production and Power Generation Biosilica to HPC and Power to the Grid • Currently Rice Hull is sent to landfills at a cost • Black ash is not suited for HPC due to high carbon content • No solid waste as inorganic matter in rice hull becomes Biosilica • Simple process easy to operate and control • Zero CARBON emissions and future carbon CREDITS • ChK Process unique features: • Biosilica Carbon content < 0.1%; NO graphitic carbon • Zero crystallinity • Produces process heat and power based on site requirements

6. Zero Carbon - Feed BIOMASS Atmosphere CO2 O2 CO2 Steam & Power O2 Photosynthesis Rice Hulls Rice Fields Rice Milling Plants Generates Rice Hulls Rice Hull Biosilica Plant Biosilica

7. 7

8. Biosilica Properties • Silica content: > 90 W% • Type: Amorphous silica • Carbon Wt%: < 0.1 W% • Cristobalite: No crystalline matter (verified in XRD and FTIR) • Major Uses: • Pozzolan additive to concrete; replaces 10 to 20% of cement • Produces ZSM-5 zeolite by thermochemical methods WITHOUT an organic template • Filler in paints, plastics and tires

9. BiosilicaHigh Performance Cement and In Architectural CementUnground Ground .

10. High Performance Concrete (HPC)Use to Mitigate Severe Erosion in Dams Kinzua Dam in Pennsylvania HPC used to mitigate severe erosion due to abrasion with water flow DOING WELL AFTER HPC INSTALLATION IN 1983

11. Addition of Biosilica in HPC Results in Slower Curing and Higher Strengths (Increase by 35%) Figure – Rate of Development of Compressive Strength in GBiosilica Concrete Figure – Comparison of the 28-Day Compressive Strength of UBiosilica and GBiosilica Concrete

12. Bridges in FloridaCorrosion concerns – State Government Specifies Addition of 8 to 9% Silica Fume in Concrete that Stands in Salt Water or Gets Splashed Bridge in Florida in US – 1 Highway • Other applications for Biosilica in HPC • Parking lots in cold climates – subjected to severe chloride corrosion from salted roadways • High rise buildings that require HPC with high modulus of elasticity

13. Biosilica Substantially Reduces Chloride Permeability Figure – Comparison of Chloride Permeability Values of Biosilica Concretes after 56-Day Curing

14. Durability Issues • Corrosion – Most Prominent Problem • Alkali-Silica Reactivity (ASR) • Delayed Ettringite Formation (DEF) • Sulfate Attack • Freeze-Thaw Damage

15. White Architectural Cement

16. Biosilica Use in ZSM-5 Production • ChK Process - patented • ChK has developed a process to minimize heating requirements without using any organic template • Synthesis conditions • Si/Al molar ratio of reaction mixture: 20 to 100 • Temperature 190°C (could use 200 LB steam for heat up) • Crystallization time 36 hours • Seeding with up to 1% ZSM 5 • Product is filtered washed and dried at 120°C. • For special applications, ZSM-5 could be calcined, as needed • Product ZSM-5 properties • Si/Al Molar ratios of 80 and above are easily obtained. • Carbon content of Rice Hull ash affects the type and quality of ZSM-5

18. Pilot Scale Rotary Calciner for BioSilica Manufacture 6 in diameter tube 20 FT long 3-Zone temperature control

19. Large (Commercial Scale) Rotary Calciner (Illustrative) 6 FT diameter tube > 60 FT long Heat input with a string of natural gas burners

20. Acknowledgements • Dr. Harish, K.V. - Clemson University, Clemson, SC • Dr. Ferraro, R. M. - University of Miami, Coral Gables, FL • Dr. Ramesh Borade • Dr. Arun Bonapati • NSF SBIR Phase II Award Number: 0724463