New Tools in the Water Technology Toolbox    Swellable Organosilica Materials forReversible Extractions of Dissolved Organ...
High Volume Waste Streams, Very Little Attention “The solution to pollution         is dilution.” When something outlasts ...
Produced Water: Energy-Water Nexus Produced water is the water from petroleum production. 800 billion gallons of produced ...
Oil Sand Production: Energy-Water Nexus Steam assisted gravity drain (SAGD) water 300 million gallons per day by 2030.
How much organic in produced water?Just considering dissolved hydrocarbon and BTEX ~ 250 ppm250 ppm x 800 billion gallons ...
How much organic in produced water?Just considering dissolved hydrocarbon and BTEX ~ 250 ppm250 ppm x 800 billion gallons ...
Aryl-Bridged Mesoporous Silica That Swells: Osorb®                                         No solvent   150 µm 200 nm     ...
Sol-Gel Derived Mesoporous SilicasSol-Gel Process           Ordered Templated Materials                           Aerogels...
Origin of Swelling BehaviorFlexibly tethered array of silica nanoparticlesDry                    Partially Swollen        ...
Characteristics of Osorb                                                                     1200                         ...
Force Generation Upon SwellingOrganic liquids                                      Hydrocarbon vapors                     ...
P ro d u c e d Wa te r Tre a tm e n tOs o rb ® re m o ve s a wid e ra n g e o f o rg a n ic s fro m wa te r:
Absorption Model                                                       hydrophobic                                        ...
Absorption Model: Solid Solvent                                                                                         Ex...
Treatment of Highly Impacted WaterPesticide waste                        Flow back waterComplex mixture of pesticides, dye...
Rare Earth Extraction from Shale Gas Water                                          Rare earths elements are not          ...
Rare Earth Extraction from Shale Gas WaterChallenge is extracting REEfrom Group II cations.Creating a type of Osorb thatdu...
Ex situ remediation: Produced water and flow back Funding from National Science Foundation and U.S. Department of Energy  ...
Stormwater Runoff Problem
Stormwater Runoff Problem
What critical materials are being lost?   Nitrate and Phosphate55% of the energy input in domesticwheat production is nitr...
Rain Garden/Bioswale/BioretentionDesigned to slow the flow of stormwater and filter pollutants fromthe water before it ev...
Rain Garden/Bioswale/Bioretention  Multiple physical, chemical, and biological functions           Limited adsorption ca...
Project Goals  Title: Development of Physico-Chemically and Biologically  Activated Swelling Organosilica-Metal Composite...
Osorb®-Metal Composites   Al-Osorb        Fe-Osorb        Mg-Osorb         Ni-Osorb   Zn-Osorb - Researched new metal-Osor...
Column Tests:Osorb®-Metal Composites Fill Media  Simulated Runoff PollutantsParameter               Pollutants           ...
Iron-Osorb® Bioretention Systems   OMR001&2 – Iron-Osorb Enviro-Swales (July 2012)                    Before             ...
Field Tests:Iron-Osorb Enhanced Bioretention SystemSite views of field-scale experimental bioretention systems (rain garde...
Column Tests:Motor Oil Removal   1000 mg/L of motor oil loading   Improved removal efficiency of motor oil with Osorb-Met...
Column Tests:Nitrate Removal   10 mg/L of NO3-N loading  Up to 50% improved removal efficiency of NO3 with Osorb-Metals
Column Tests:Phosphate Removal   10 mg/L of PO4-P loading66 Up to 40% improved removal efficiency of PO4 with Osorb-Metals
Column Tests:Atrazine Removal   500 µg/L of atrazine loading Up to 60% improved removal efficiency of atrazine with Osorb...
Column Tests:Hormone Reduction
Field Tests:Nutrient Removal    Lower effluent concentration of nutrients from iron-Osorb    enhanced rain garden compared...
Column Tests:Soil Microbial Community Scanning electron microscope (SEM) images of soil mix control (a) and Fe-Osorb amend...
What is Next? Currently developing a magnetically retrievable phosphate selective binding Osorb to amend agricultural bios...
Philadelphia is taking the lead!Green City, Clean Waters PlanAdministrator Lisa Jackson and Mayor Michael Nutter announced...
Acknowledgements and References Support:  National Science Foundation  U.S. Department of Energy  Ohio EPA Collaborators: ...
Permeability to Organics vs. Water Vapor                                                  7                               ...
ACS Symposium: New Tools in the Water Technology Toolbox Swellable Organosilica Materials for Reversible Extractions of Di...
Upcoming SlideShare
Loading in …5
×

ACS Symposium: New Tools in the Water Technology Toolbox Swellable Organosilica Materials for Reversible Extractions of Dissolved Organics and Metals

1,436 views

Published on

By Paul Edmiston, College of Wooster

Published in: Technology, Business
0 Comments
0 Likes
Statistics
Notes
  • Be the first to comment

  • Be the first to like this

No Downloads
Views
Total views
1,436
On SlideShare
0
From Embeds
0
Number of Embeds
141
Actions
Shares
0
Downloads
9
Comments
0
Likes
0
Embeds 0
No embeds

No notes for slide

ACS Symposium: New Tools in the Water Technology Toolbox Swellable Organosilica Materials for Reversible Extractions of Dissolved Organics and Metals

  1. 1. New Tools in the Water Technology Toolbox Swellable Organosilica Materials forReversible Extractions of Dissolved Organics and Metals Paul L. Edmiston College of Wooster Contact Information: pedmiston@wooster.edu ACS Fall Meeting 2012, Philadelphia, PA Ensuring the Sustainability of Critical Materials and Alternatives
  2. 2. High Volume Waste Streams, Very Little Attention “The solution to pollution is dilution.” When something outlasts a certain degree of usefulness, we wish it to disappear. Since matter cannot be destroyed, a convenient disposal method is dilution. Two high volume waste streams that are hard to dilute due to volume, but may hold great resource potential: 1. Produced Water 2. Stormwater Runoff
  3. 3. Produced Water: Energy-Water Nexus Produced water is the water from petroleum production. 800 billion gallons of produced water every year. Current practice onshore: Reinjection Current Practice off-shore: Overboard Average 10 water: 1 oil ratio Produced water contains: dissolved organics production chemicals NORMS organic acids metals ions salt
  4. 4. Oil Sand Production: Energy-Water Nexus Steam assisted gravity drain (SAGD) water 300 million gallons per day by 2030.
  5. 5. How much organic in produced water?Just considering dissolved hydrocarbon and BTEX ~ 250 ppm250 ppm x 800 billion gallons = 250 million gal of gasoline eq. Enough gasoline to supply U.S. needs for 1 day.**U.S. Energy Administration http://www.eia.gov/tools/faqs/faq.cfm?id=23&t=10
  6. 6. How much organic in produced water?Just considering dissolved hydrocarbon and BTEX ~ 250 ppm250 ppm x 800 billion gallons = 250 million gal of gasoline eq. Enough gasoline to supply U.S. needs for 1 day.* Extraction of dissolved components has a substantial thermodynamic barrier. Need to overcome entropy.*U.S. Energy Administration http://www.eia.gov/tools/faqs/faq.cfm?id=23&t=10
  7. 7. Aryl-Bridged Mesoporous Silica That Swells: Osorb® No solvent 150 µm 200 nm +Solvent OCH3 H3 CO Si CH2CH2 OCH3 OCH3 CH2 CH2 Si OCH3 OCH3Surface area: 400-600 m2/gPore volume: 0.6-1.5 mL/g
  8. 8. Sol-Gel Derived Mesoporous SilicasSol-Gel Process Ordered Templated Materials Aerogels Polysilsesquioxanes
  9. 9. Origin of Swelling BehaviorFlexibly tethered array of silica nanoparticlesDry Partially Swollen Fully Swollen 200 nm 150 nm 200 nm Gelation Crosslink Derivatize/Dry
  10. 10. Characteristics of Osorb 1200 Volume Adsorbed cc/g (STP) 1000 800 600 400 200 0 0 0.5 1 Relative Pressure Ps/Po ® Surface Area and Pore Volumes of Various Osorb Materials Swell Surface Pore Pore Size Distribution (%) 2Type mL/g Area(m /g) Volume (mL/g) under 6 nm 6-8 nm 20-80 nm 1 5.2 885 2.85 6 8 68 2 9.8 416 0.57 48 22 - 3 4.6 171 0.27 98 - - 4 2.5 803 0.98 20 15 38
  11. 11. Force Generation Upon SwellingOrganic liquids Hydrocarbon vapors propane 600 liquid = acetone 500Force N/g 400 300 200 methane 100 0 0 1 2 3 4 Volume increase (v/v) Max force 600 N/g (61,000 w/w) Work = 0.8 ± 0.1 J/g ΔHswell = 5.2 ± 1.2 J/g Entropically driven process Max 1x w/w change for condensable 300% ΔV, 650% Δmass vapors when p=p0 13% volume,
  12. 12. P ro d u c e d Wa te r Tre a tm e n tOs o rb ® re m o ve s a wid e ra n g e o f o rg a n ic s fro m wa te r:
  13. 13. Absorption Model hydrophobic barrier1 Matrix tension 2 void volume new surface area Dissolved hydrocarbons3 4 Continued matrix expansion
  14. 14. Absorption Model: Solid Solvent Extra c tio n o f 30 Co m p o u n d sOs o rb ® a c ts a s a “s o lid s o lve n t” th a t u s e s b y Os o rb vs . lo g Ko wm e c h a n ic a l re la xa tio n a s a n a d d itio n a l d rivin gfo rc e fo r a b s o rp tio n o f o rg a n ic s fro m wa te r.Expansion is endothermic indicating a decrease inentropy (∆Smatrix) that is a significant energy termmanifested by fact that swelling can producemechanical forces that exceed 400N/g.In g e n e ra l, th e re is a o n e o rd e r o f m a g n itu d eg re a te r p a rtitio n c o e ffic ie n t fo r a b s o rp tio n b yOs o rb c o m p a re d to liq u id -liq uid e xtra c tio n d u e k = Osorb/water equilibrium partition coefficientto th e c o n trib u tio n fro m m a trix e xp a n s io n . Kow = octanol-water partition coefficient Conditions : contaminant concentration 100 ppm, 0.5% w/v Osorb per volume of solution, T=25°C.
  15. 15. Treatment of Highly Impacted WaterPesticide waste Flow back waterComplex mixture of pesticides, dyes, TOC before = 265 ppmBTEX, surfactants TOC after = no detect(5% organics by weight) 0.4%w/v Osorb
  16. 16. Rare Earth Extraction from Shale Gas Water Rare earths elements are not rare, but formations of high concentration are hard to find. Found in alluvial deposits where freshwater meets salt water. Ideal location would be in ancient estuary environments. Many are buried in shale deposits. Hydraulic fracking is exploring deep shale deposits. Utica shale shows regions where rare earth element concentrations are in excess of 4,000 ppm. Exploring synergistic extraction of REEs and hydrocarbons in PW
  17. 17. Rare Earth Extraction from Shale Gas WaterChallenge is extracting REEfrom Group II cations.Creating a type of Osorb thatduplicates the multistageliquid-liquid extraction processuse in conventionalhydrometallurgical processesin a single core-shell particleGoals:1) Rapid sampling system using hand-held XRF2) Larger scale extraction system for PW.
  18. 18. Ex situ remediation: Produced water and flow back Funding from National Science Foundation and U.S. Department of Energy for pilot scale testing in the field, produced water and flow backTrailer and Skid-Mounted Systems Available (4-60 gal/min)Skid system tested by Texas A&M University
  19. 19. Stormwater Runoff Problem
  20. 20. Stormwater Runoff Problem
  21. 21. What critical materials are being lost? Nitrate and Phosphate55% of the energy input in domesticwheat production is nitrate fertilizer Economical supplies of phosphate areWoods J et al. Phil. Trans. R. Soc. B 2010;365:2991-3006 limited and can be depleted.
  22. 22. Rain Garden/Bioswale/BioretentionDesigned to slow the flow of stormwater and filter pollutants fromthe water before it eventually recharges ground water, seeps intothe municipal storm sewer system, or discharge into waterways Rain Garden, Bioswale, Bioretention System, Bioinfiltration System, Biofilter, Stormwater Wetland, Vegetated Buffer System
  23. 23. Rain Garden/Bioswale/Bioretention  Multiple physical, chemical, and biological functions  Limited adsorption capacity: - Short retention time - Poor removal of soluble pollutants - Not recommended at “hot spots”
  24. 24. Project Goals  Title: Development of Physico-Chemically and Biologically Activated Swelling Organosilica-Metal Composites Filter Media in Bioretention Systems for Enhanced Remediation of Urban and Agricultural Stormwater Runoff  Hypothesis: Properly amended Osorb-metal composites filter media in bioretention systems can remove a wide variety of stormwater runoff pollutants and significantly enhance overall treatment capacity of the systems  Work Plan: Develop Osorb-based materials with embedded reactive metal particles including aluminum (Al0), iron (Fe0), magnesium (Mg0), zinc (Zn0), and nickel (Ni0) to capture organic pollutants and chemically degrade pollutants from runoff water
  25. 25. Osorb®-Metal Composites Al-Osorb Fe-Osorb Mg-Osorb Ni-Osorb Zn-Osorb - Researched new metal-Osorb composites - Examined reduction of motor oil, nitrate, phosphate, atrazine, estradiol, triclosan, and ethylene glycol - Continue research to determine reduction mechanism and longevity in Phase II funding
  26. 26. Column Tests:Osorb®-Metal Composites Fill Media  Simulated Runoff PollutantsParameter Pollutants Concentration (mg/LPetrolum hydrocarbons Motor oil 1000 1000Nutrients Nitrate (NO3-N) 20 10 Phosphate (PO4-P) 10 10Herbicide Atrazine (C8H14ClN5) 1 0.5Pharmaceuticals 17α-Ethinylestradiol (C20H24O2) 1 0.5 Triclosan (C12H7Cl3O2) 0.5 1Antifreeze/deicer Ethylene glycol (C2H6O2) 1000 1000 Experimental Set-Up  A total of seven simulated runoff event once a week  Different contents (0%, 1%, 2%) of three Osorb-metals (Fe, Mg, and Zn) in soil base media: sand or soil mix
  27. 27. Iron-Osorb® Bioretention Systems  OMR001&2 – Iron-Osorb Enviro-Swales (July 2012) Before After Before After
  28. 28. Field Tests:Iron-Osorb Enhanced Bioretention SystemSite views of field-scale experimental bioretention systems (rain gardens) installed at the campus of theCollege of Wooster, OH. One is a standard model, and one version is enhanced with Iron-Osorb.
  29. 29. Column Tests:Motor Oil Removal  1000 mg/L of motor oil loading Improved removal efficiency of motor oil with Osorb-Metals
  30. 30. Column Tests:Nitrate Removal  10 mg/L of NO3-N loading Up to 50% improved removal efficiency of NO3 with Osorb-Metals
  31. 31. Column Tests:Phosphate Removal  10 mg/L of PO4-P loading66 Up to 40% improved removal efficiency of PO4 with Osorb-Metals
  32. 32. Column Tests:Atrazine Removal  500 µg/L of atrazine loading Up to 60% improved removal efficiency of atrazine with Osorb-Metals
  33. 33. Column Tests:Hormone Reduction
  34. 34. Field Tests:Nutrient Removal Lower effluent concentration of nutrients from iron-Osorb enhanced rain garden compared to standard rain garden
  35. 35. Column Tests:Soil Microbial Community Scanning electron microscope (SEM) images of soil mix control (a) and Fe-Osorb amended soil mix (b) in the saturated bioretention design after the completion of 3-month column experiments. Blue arrows indicate bacteria or other microorganisms.
  36. 36. What is Next? Currently developing a magnetically retrievable phosphate selective binding Osorb to amend agricultural bioswales for phosphate recovery and watershed protection.
  37. 37. Philadelphia is taking the lead!Green City, Clean Waters PlanAdministrator Lisa Jackson and Mayor Michael Nutter announced April 10, 2012 that the EPAand Philadelphia will join in advancing the use of cutting-edge green infrastructure technologiesto solve the city’s sewage overflows and create healthier neighborhoods for the city’s residents.The agreement specifically highlights Philadelphia’s capacity to serve as a model for citiesnationwide to embrace green infrastructure to manage stormwater runoff.
  38. 38. Acknowledgements and References Support: National Science Foundation U.S. Department of Energy Ohio EPA Collaborators: Dr. Hanbae Yang Edmiston, P. L.; Underwood, L. A. Absorption of Dissolved Organic Dr. Tatiana Eliseeva Speciestion a nd P urifica tionOrganically Modified Silica(2009). S e pa ra from Water Using Te chnology 66, 532-540 that Swells. Dr. Stephen Jolly Burkett, C. M.*; Underwood, L. A.*, Volzer, R. S.*; Baughman, J. A.*; Justin Keener Edmiston, P. L. Organic-Inorganic Hybrid Materials that Rapidly Swell in Non-Polar Liquids: Nanoscale Morphology and Swelling Mechanism. Che mis try of Ma te ria ls 20, 1312-1321 (2008). Students: Burkett, C. M.; Edmiston P. L.; Highly Swellable Sol-Gels Prepared by Zachary Harvey Chemical Modification of Silanol Groups Prior to Drying. J Non-Crys ta lline S olids ,351 , 3174-3178 (2005). Alison Chin Edmiston, P.L.; Campbell, D.P.; Gottfried, D.S.; Baughman, J.*; Timmers, Noel Mellor M.M.* Detection of Trinitrotoluene in the Parts-per-Trillion Range Using Waveguide Interferometry, S e ns or & Actua tors B. 143, 574-582 (2010). Christine Kasprisin Melissa Morgan www.absmaterials.com Paige Piper pedmiston@wooster.edu 330-234-7999
  39. 39. Permeability to Organics vs. Water Vapor 7 Infrared Absorbance in Collection 6 propane 5 Chamber 4 3 2 1 H 2O 8 mm 1 mm 0 0 10 20 30 40 50 60 Time (min) IR spectrometer Osorb disk Gas cell Vent (100 mL) Propane + H2O(g)sat N2, 1 mL/minDiffusion cell – Osorb separated flow cells

×