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Biosilica
    for Manufacturing
      and Applications

          ChK Group, Inc.
             Plano, Texas




       Rajan K. Vempati, Ph.D.
Subbaraman Viswanathan, Ph.D.
Biosilica a Premium Additive in
              High Performance Concrete (HPC)
                           Value Chain for Biosilica

                            ChK Process
Rice                                                     Biosilica to
                            Biosilica
Cultivation                                              HPC use
                            Production
Processing in                                            Power to the
                            Power
RICE MILLS                                               Grid
                            Generation
 Currently        ChK Process unique            •   No solid waste as
  Rice Hull is     features:                         inorganic matter in
  sent to                                            rice hull becomes
                   •   Biosilica Carbon
  landfills at a                                     Biosilica
                       content < 0.1% with
  cost
                       NO graphitic carbon       •   Simple process easy to
 Black ash is
                   •   Zero crystallinity with       operate and control
  not suited
  for HPC due
                       no cristobalite           •   Zero CARBON
  to high          •   Produces process heat         emissions and future
  carbon               and power based on            carbon CREDITS
  content              site requirements
Zero Carbon – With Bio-Material Use
(Produces Green Construction Material and Power)

                    Atmosphere


O2       CO2
                                           CO2
                                 O2
Photosynthesis                                                     Steam & Power
                                   Rice
  Rice Fields                      Hulls

                  Rice Milling Plants              Rice Hull
                 Generates Rice Hulls            Biosilica Plant



                                                 Biosilica
Biosilica
            Renewable Cementitious Material

                                            Rice Hull
                                         From Rice Mills




 Rice Field
(Upland Cultivation)
Supply of Rice Hulls
       Agricultural Waste Generated by the Rice Milling Industry
       No Real Value: Most Uses Never Cover the Cost of Transportation
       Supply Potential                                     Rice Hull Properties

                                                    HHV Dry Basis     16.2
                                     Silica
            Rice        Bio Silica
                                     Fume           MJ/Kg             [6,965 BTU/LB]
           Actual       Potential    Actual
           Ton/Yr        Ton/Yr      Ton/Yr
                                                    Moisture, W%      9.7%

 USA       10,500,000      378,000    60,000*
                                                    Volatile, W%      66%
                                                    Carbon, W% MF     40.2%
GLOBAL    550,000,000   19,800,000
                                                    Ash, W%           18.2%
   Most of this silica fume is imported
                                                    Ash Composition
                                                    SiO2 –W% 89 to 95%; Al2O3 0.41
                                                    Fe2O3 0.25; CaO 0.75%; MgO 0.43
                                                    K2O 2.2%
                                                5
Biosilica Properties
• Silica content:        > 90w%
• Type:                  Amorphous silica
• Carbon Wt%:            < 0.1 W%
• Cristobalite Wt%: Not Detected Crystalline Silica
• 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 and plastics
Biosilica
High Performance Cement and In Architectural Cement
      Unground                     Ground   .
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
Addition of Biosilica in HPC Results in Slower
Curing and Higher Strengths (Increase by 35%)
Bridges in Florida
Corrosion 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
Biosilica Substantially Reduces
    Chloride Permeability
The ChK Process
                            For Biosilica Production




                                                                               Scrubber and
                                                      Thermal
                                                      Oxidizer to Stack
                                2 Energy
                                                                          1




                                                                               Stack
                                 Options              Steam Boiler/
                                                      Turbine-Power
                                                      2
                                                      Pyrolysis oil        2
                                                      Refining to diesel..
                                                                            Refinery
                                         Partial                            Upgrading
                                         Oxidation
                   Drying    Dried       Pyrolysis and
Rice Hull          150 oC    Rice Hull   Gasification    Biosilica
                                         < 700 oC

Natural gas and
Recycle fuel gas                                    Water/
                                                    Steam
Combustion Air
Pilot Scale Rotary Calciner for BioSilica
Manufacture




                                   6 in diameter tube
                                   20 FT long 3-Zone
                                      temperature
                                         control
Large (Commercial Scale) Rotary Calciner (Illustrative)


                                     6 FT diameter tube
                                         > 60 FT long
                                   Heat input with a string
                                    of natural gas burners
Future Plans
• Biosilica and Energy Corporation (BsEC) formed to commercialize
  the ChK Process
• Seeking investors to construct the first commercial plant
• Plant payback in less than 5 years
• Contacts:


    Rajan K. Vempati, Ph.D.
    President, ChK Group, Inc.
    Phone: (214) 704-4128; e-Mail: chkgroup@att.net
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
Acknowledgements
• Dr. Prasad Rangaraju - Clemson University, Clemson, SC
• Dr. Harish, K.V. - Clemson University, Clemson, SC
• Dr. Antonio Nanni - University of Miami, Coral Gables, FL
• Dr. Ferraro, R. M. - University of Miami, Coral Gables, FL
• Dr. Ramesh Borade
• Dr. Arun Bonapati - Harper International, Inc., Lancaster, NY


• NSF SBIR Phase II Award Number: 0724463

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Biosilica acs

  • 1. Biosilica for Manufacturing and Applications ChK Group, Inc. Plano, Texas Rajan K. Vempati, Ph.D. Subbaraman Viswanathan, Ph.D.
  • 2. Biosilica a Premium Additive in High Performance Concrete (HPC) Value Chain for Biosilica ChK Process Rice Biosilica to Biosilica Cultivation HPC use Production Processing in Power to the Power RICE MILLS Grid Generation  Currently ChK Process unique • No solid waste as Rice Hull is features: inorganic matter in sent to rice hull becomes • Biosilica Carbon landfills at a Biosilica content < 0.1% with cost NO graphitic carbon • Simple process easy to  Black ash is • Zero crystallinity with operate and control not suited for HPC due no cristobalite • Zero CARBON to high • Produces process heat emissions and future carbon and power based on carbon CREDITS content site requirements
  • 3. Zero Carbon – With Bio-Material Use (Produces Green Construction Material and Power) Atmosphere O2 CO2 CO2 O2 Photosynthesis Steam & Power Rice Rice Fields Hulls Rice Milling Plants Rice Hull Generates Rice Hulls Biosilica Plant Biosilica
  • 4. Biosilica Renewable Cementitious Material Rice Hull From Rice Mills  Rice Field (Upland Cultivation)
  • 5. Supply of Rice Hulls Agricultural Waste Generated by the Rice Milling Industry No Real Value: Most Uses Never Cover the Cost of Transportation Supply Potential Rice Hull Properties HHV Dry Basis 16.2 Silica Rice Bio Silica Fume MJ/Kg [6,965 BTU/LB] Actual Potential Actual Ton/Yr Ton/Yr Ton/Yr Moisture, W% 9.7% USA 10,500,000 378,000 60,000* Volatile, W% 66% Carbon, W% MF 40.2% GLOBAL 550,000,000 19,800,000 Ash, W% 18.2% Most of this silica fume is imported Ash Composition SiO2 –W% 89 to 95%; Al2O3 0.41 Fe2O3 0.25; CaO 0.75%; MgO 0.43 K2O 2.2% 5
  • 6. Biosilica Properties • Silica content: > 90w% • Type: Amorphous silica • Carbon Wt%: < 0.1 W% • Cristobalite Wt%: Not Detected Crystalline Silica • 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 and plastics
  • 7. Biosilica High Performance Cement and In Architectural Cement Unground Ground .
  • 8. 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
  • 9. Addition of Biosilica in HPC Results in Slower Curing and Higher Strengths (Increase by 35%)
  • 10. Bridges in Florida Corrosion 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
  • 11. Biosilica Substantially Reduces Chloride Permeability
  • 12. The ChK Process For Biosilica Production Scrubber and Thermal Oxidizer to Stack 2 Energy 1 Stack Options Steam Boiler/ Turbine-Power 2 Pyrolysis oil 2 Refining to diesel.. Refinery Partial Upgrading Oxidation Drying Dried Pyrolysis and Rice Hull 150 oC Rice Hull Gasification Biosilica < 700 oC Natural gas and Recycle fuel gas Water/ Steam Combustion Air
  • 13. Pilot Scale Rotary Calciner for BioSilica Manufacture 6 in diameter tube 20 FT long 3-Zone temperature control
  • 14. Large (Commercial Scale) Rotary Calciner (Illustrative) 6 FT diameter tube > 60 FT long Heat input with a string of natural gas burners
  • 15. Future Plans • Biosilica and Energy Corporation (BsEC) formed to commercialize the ChK Process • Seeking investors to construct the first commercial plant • Plant payback in less than 5 years • Contacts: Rajan K. Vempati, Ph.D. President, ChK Group, Inc. Phone: (214) 704-4128; e-Mail: chkgroup@att.net
  • 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
  • 17.
  • 18. Acknowledgements • Dr. Prasad Rangaraju - Clemson University, Clemson, SC • Dr. Harish, K.V. - Clemson University, Clemson, SC • Dr. Antonio Nanni - University of Miami, Coral Gables, FL • Dr. Ferraro, R. M. - University of Miami, Coral Gables, FL • Dr. Ramesh Borade • Dr. Arun Bonapati - Harper International, Inc., Lancaster, NY • NSF SBIR Phase II Award Number: 0724463