OLI 24th Users Conference October 24,2007

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Presentation transcript:

OLI 24th Users Conference October 24,2007 Applying Electrolyte Theory To Real World Problems Noel C. Scrivner DuPont Fellow (Retired) Adjunct Professor ChE Rowan University (Active) 10/24/07 OLI 24th Users NC Scrivner

OLI 24th Users NC Scrivner Topics Fluoride removal Cr+3 removal Graphical techniques for understanding 10/24/07 OLI 24th Users NC Scrivner

Waste Treatment Plant for Acidic Fluoride Stream Environmental requirements pH 6 to 9 range ”Total” fluoride (dissolved & suspended) low teens Feed stream pH 2 to 3 Fluoride 1,000 ppm Lime slurry at site for neutralization ESP simulation shows 8 ppm Fluoride over 6 to 9 pH range Small scale pilot of system for other reasons 10/24/07 OLI 24th Users NC Scrivner

OLI 24th Users NC Scrivner 10/24/07 OLI 24th Users NC Scrivner

OLI 24th Users NC Scrivner 10/24/07 OLI 24th Users NC Scrivner

OLI 24th Users NC Scrivner Pilot Plant Results Smooth operation Controlled pH 8 to 9 range Fluoride < 10 ppm Met other requirements Towards end of scheduled operation Fluoride increases to 20 ppm Ran low on lime, went to Newark Farm & Home for 40 lb bag of Dolomitic lime What could be happening ? 10/24/07 OLI 24th Users NC Scrivner

Critical Stability Constants CaF+ & MgF+ Complexes and CaF2 & MgF2 ppt 10/24/07 OLI 24th Users NC Scrivner

OLI 24th Users NC Scrivner ESP Model changes Added Mg(OH)2 to chemistry generation file Dolomitic Lime 10% Mg(OH)2 & 90% Ca(OH)2 New simulation Predicted total fluoride about 20 ppm in 6 to 9 pH range 10/24/07 OLI 24th Users NC Scrivner

OLI 24th Users NC Scrivner 10/24/07 OLI 24th Users NC Scrivner

OLI 24th Users NC Scrivner MgF2 ppt does not form Add more dolomitic line for CaF2 ppt formation Too high pH from Mg(OH)2 Stoichiometric Ca 10/24/07 OLI 24th Users NC Scrivner

OLI 24th Users NC Scrivner Learnings Don’t use Dolomitic Line at the plant Need full and correct list of feed chemicals Go to the literature for leads on additional chemistry to include in the ESP model Need a complete and correct database Need both ESP simulation and experiments Chemistry is still an experimental science 10/24/07 OLI 24th Users NC Scrivner

OLI 24th Users NC Scrivner Chromium Problem Wastewater from CrO2 process Chromium concentration > 50 ppm Soluble Cr(VI) as CrO4 = anion Reduce total Chromium to < 1ppm 10/24/07 OLI 24th Users NC Scrivner

OLI 24th Users NC Scrivner Process Reduce Cr+6 to Cr+3 Reducing agent HSO3- Reduction kinetics fast at low pH Form Cr(OH)3 precipitate at high pH 10/24/07 OLI 24th Users NC Scrivner

Reactions & Soluble Chromium Species Cr(OH)3 PPT = Cr+3 + 3 OH- Cr+3 + OH- = Cr(OH)+2 Cr(OH)+2 + OH- = Cr(OH)2+ Cr(OH)2+ + OH- = Cr(OH)3 AQ Cr(OH)3 AQ + OH- = Cr(OH)4- 10/24/07 OLI 24th Users NC Scrivner

OLI 24th Users NC Scrivner 10/24/07 OLI 24th Users NC Scrivner

Metal Hydroxide Solubility Data Literature values vary Experimental method Complexing agents Particle size Age 10/24/07 OLI 24th Users NC Scrivner

OLI 24th Users NC Scrivner 10/24/07 OLI 24th Users NC Scrivner

OLI 24th Users NC Scrivner 10/24/07 OLI 24th Users NC Scrivner

Results from other programs Cr+3 system Cu+2 system Zn+2 system 10/24/07 OLI 24th Users NC Scrivner

OLI 24th Users NC Scrivner XXXXX xxxxx 10/24/07 OLI 24th Users NC Scrivner

OLI 24th Users NC Scrivner xxxxx ====== 10/24/07 OLI 24th Users NC Scrivner

OLI 24th Users NC Scrivner XXXXX ===== 10/24/07 OLI 24th Users NC Scrivner

OLI 24th Users NC Scrivner Conclusions Use theory to suggest which species could be important If these are not in the database, could be problems Check other sources for data & do a hand calculation Include all possible feed compounds in the chemistry model Use the model to suggest critical experiments 10/24/07 OLI 24th Users NC Scrivner

What else have I learned ? Garbage In => Garbage Out The purpose of computing is insight not numbers 10/24/07 OLI 24th Users NC Scrivner

OLI 24th Users NC Scrivner 10/24/07 OLI 24th Users NC Scrivner

What else have I learned ? Garbage In => Garbage Out The purpose of computing is insight not numbers Show the big picture to clients & peers (and yourself) “Flood” plots “Sillen” plots 10/24/07 OLI 24th Users NC Scrivner

OLI 24th Users NC Scrivner 10/24/07 OLI 24th Users NC Scrivner

OLI 24th Users NC Scrivner 10/24/07 OLI 24th Users NC Scrivner

OLI 24th Users NC Scrivner Flood Plot for Diprotic System pH from adding only CO2 or NaHCO3 or Na2CO3 Most “Flood” lines not shown pKa1=6.35 pKa2=10.33 10/24/07 OLI 24th Users NC Scrivner

OLI 24th Users NC Scrivner 10/24/07 OLI 24th Users NC Scrivner

OLI 24th Users NC Scrivner 10/24/07 OLI 24th Users NC Scrivner

OLI 24th Users NC Scrivner 10/24/07 OLI 24th Users NC Scrivner

OLI 24th Users NC Scrivner CO2 HCO3- CO3= OH- H+ 10/24/07 OLI 24th Users NC Scrivner

OLI 24th Users NC Scrivner 10/24/07 OLI 24th Users NC Scrivner

OLI 24th Users NC Scrivner Conclusions Consider the Chemistry Check other data sources Uncertainty Analysis Purpose is insight not pages of output Experiments to Confirm 10/24/07 OLI 24th Users NC Scrivner