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by Keith Taylor Department of Chemistry and Biochemistry

By-Product From the Lowly Soybean Creates Jobs and Saves the Planet Canada - Mexico Water Workshop March 30, 2010. by Keith Taylor Department of Chemistry and Biochemistry. People & Money. Collaborators J.K. Bewtra and N. Biswas, Civil & Environmental Engineering Recent Students

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by Keith Taylor Department of Chemistry and Biochemistry

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  1. By-Product From the Lowly Soybean Creates Jobs and Saves the PlanetCanada - Mexico Water Workshop March 30, 2010 by Keith Taylor Department of Chemistry and Biochemistry

  2. People & Money Collaborators • J.K. Bewtra and N. Biswas, Civil & Environmental Engineering Recent Students • Katy Modaressi • Beeta Saha • Aaron Steevensz • Mohammad Mousa Al-Ansari • Ram Mantha • Joey Patapas Funding • Natural Sciences and Engineering Research Council • Ontario Ministry of Agriculture and Food Canada - Mexico Water Workshop March 30, 2010

  3. Introduction Wastewater – Process Water Phenolic and aryl amine compounds in process- and wastewater streams from various industries such as: • petroleum refining. • coal conversion • wood products & preseservation. • metal casting. • pulp, paper, dyes, resin, plastics and textiles manufacturing. These compounds are considered to be toxic and have been classified as hazardous pollutants. Canada - Mexico Water Workshop March 30, 2010

  4. Phenols in Solution enzyme + oxidant Oligomer/Polymer (separate solid) Capture solid precipitate, use as pre-adhesive, etc. Immobilize solid on soil organic matter (Bollag) Water Treatment Strategy Canada - Mexico Water Workshop March 30, 2010

  5. Enzyme-based Wastewater Treatment • Capture organic material in minimally-modified form • Remediation but not degradation • Enabling technology: availability of enzymes as commodities (peroxidases, but not HRP, and laccases) • By recombinant fermentation techniques (ARP, laccase) • Cheaper wild-type sources (SBP) • Cost-effective? Canada - Mexico Water Workshop March 30, 2010

  6. Advantages of Enzyme-Based Treatment Advantages over conventional biological treatment: • Easy to handle and store; simpler process control • High and low concentrations of contaminant • No shock loading effects • Broad range of pH and temperature • Contact time of seconds to minutes, small footprint • Reduced burden on biox plant and gravity separators Advantages over chemical/physical treatments: • High specificity and efficiency in removing target pollutants • Operation under milder, less corrosive, conditions • Reduced consumption of oxidants, sludge formation Canada - Mexico Water Workshop March 30, 2010

  7. Enzymes Laccase SBP - Fungal source - Requires molecular oxygen • Crude extract from seed hulls • Requires hydrogen peroxide

  8. Oxidase-catalyzed Phenol Removal(Klibanov, Bollag) Canada - Mexico Water Workshop March 30, 2010

  9. Experimental Parameters • substrates at 1.0 mM (94 ppm for parent, 128 ppm for chloroderivatives) • examine: • pH effect • enzyme dose (activity “units”/mL = U/mL) • peroxide stoichiometry • influence of PEG in reaction, alum in settling • (reactor design) • analysis by UV and colorimetric tests; HPLC Canada - Mexico Water Workshop March 30, 2010

  10. Minimum Enzyme Concentrations (U/mL) Canada - Mexico Water Workshop March 30, 2010

  11. Operating Cost - Incremental, but Offset • Water Environment Research 73 165 (2001) with ARP • 600 bbl/h@100 ppm phenols; 100 m3/h with 10kg/h phenols • SBP needed at 0.5 MU/m3; 50 MU/h; $100/h* • Peroxide required at $0.25/m3 for treatment, possibly $0.25/m3 for additive (eg. PEG or surfactant); ca. $50/h • Expendables cost, $150/h ($0.25/bbl) • *Could SBP be produced at a profit for $2/MU?? Canada - Mexico Water Workshop March 30, 2010

  12. Continuous-flow System for PhenolWater Environment Research 73 165 (2001) Canada - Mexico Water Workshop March 30, 2010

  13. Broadening the Scope • Convert other aromatics into phenols or anilines • Chemical ‘front end’ for the enzymic process • For nitro- and azo-aromatics: zero-valent iron to produce anilines • For unfunctionalized aromatics (BTEX) hydroxylation (via limited Fenton reaction) to phenols Canada - Mexico Water Workshop March 30, 2010

  14. Save the Planet? Jobs Too? • Refinery case: 5 MU/kg phenol, a bit much; $2/MU, a bit low • Processing at higher [phenol], eg. 2000 ppm, more efficient, 1.5 mU/kg • room to pay more for enzyme? • SBP is in the seedcoat, the first thing stripped off before beans are crushed for oil and protein • SBP easily extracted with water; remaining hull still as good a fibre source for animal feed • Value of hulls more than doubled • A business opportunity! Canada - Mexico Water Workshop March 30, 2010

  15. Lots of Cheap SBP • 120,000 tonnes of hulls in Ontario (Michigan, two-thirds; Iowa, 4-fold) • Could they be “borrowed”, or “rented”, to extract SBP? • Trillions of U of catalytic activity (many refineries!) • Costs: “rent”, concentrating extract, re-drying hulls • Environmental stewardship of the petroleum economy aided by bioproducts • Including non-conventional sources: oil sands, oil shale, upgrading by-products (stranded carbon), coal gasification Canada - Mexico Water Workshop March 30, 2010

  16. Save the Planet Improve existing refinery aqueous streams with a green process Begin to address air emissions by capture and treatment Products of enzyme-based treatment captured and used Optimal and responsible use of existing carbon sources Canada - Mexico Water Workshop March 30, 2010

  17. Typical Batch Reactor Data: pH Effect(phenol, 1.0 mM; peroxide,1.2 mM; PEG, 400 mg/L) Canada - Mexico Water Workshop March 30, 2010

  18. Typical Batch Reactor Data: Enzyme Dose(phenol, 1.0 mM; peroxide,1.2 mM) Canada - Mexico Water Workshop March 30, 2010

  19. Anilines, analogously Canada - Mexico Water Workshop March 30, 2010

  20. Zero-valent Iron Reduction of Nitrobenzene (Agrawal & Tratnyek, 1996) (also, azobenzene + Feo aniline; Weber, 1996) Canada - Mexico Water Workshop March 30, 2010

  21. Combined Strategy for Nitroaromatics Canada - Mexico Water Workshop March 30, 2010

  22. Unfunctionalized Aromatics • The Pollutant • BTEX (Benzene, Toluene, Ethylbenzene and Xylene) Models for others (PAHs, PCBs, dioxins and furans) • Wastewater Source • Petroleum industry • Solvent for organic synthesis • The Problem • Effect on humans • Release to environment Canada - Mexico Water Workshop March 30, 2010

  23. Fenton Reaction • Hydroxyl radical a strong oxidant • Fenton reagent often used for mineralization of organics • Can we limit it to hydroxylation? Canada - Mexico Water Workshop March 30, 2010

  24. Toluene – limited Fenton reaction Canada - Mexico Water Workshop March 30, 2010

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