McIlvaine Hot Topic Hour Evaporation and Crystallization of FGD Wastewater. September 3, 2009

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McIlvaine Hot Topic Hour Evaporation and Crystallization of FGD Wastewater September 3, 2009

Innovative Process Solutions Utilizing Evaporation & Crystallization as Core technologies

ZLD for FGD as practiced today A2A S.p.A. (formerly Endesa Italia) Monfalcone Power Plant, Italy 336 MW Coal-Fired w/ LSFO Scrubber (MHI) ZLD Operational Summer 2008 Dry Cake for Landfill Disposal Brine Evaporator Brine Crystallizer Lime-Soda Softener

Three Major Unit Operations A Softening System to reduce the overall solids and hardness content down to a level that is manageable for the evaporation system. A Falling Film Evaporator (MVR) to remove the major portion of water from the FGD purge stream. A Crystallizer (usually steam, can be MVR) to finish the process by removing the remainder of the water. Chemicals Power Steam FGD Purge Softening System Evaporator Crystallizer Salts Sludge Recovered Water

Requires chemicals, power & steam, produces sludge

Softening aids crystallization Softening FGD wastewater with lime and soda ash substitutes sodium ions for most of the calcium and magnesium ions. CaCl2 and MgCl2 have very high solubility difficult to crystallize out. Softening changes the chemistry of FGD wastewater to NaCl, which crystallizes easily.

Softening Reactions Mg +2 + Ca(OH) 2 Mg(OH) 2 + Ca +2 (lime) (sludge) Ca +2 + Na 2 CO 3 CaCO 3 + 2 Na +1 (soda ash) (sludge)

FGD ZLD Current Practice Soften the FGD purge - create a NaCl based chemistry Lime and Soda Ash Electric Power Recovered water Steam and/or Electric Power FGD purge CaCl2-MgCl2 Chemistry Softening NaCl Chemistry Brine Concentrator Evaporator Blowdown NaCl Crystallizer Centrifuge or Filter CaCO3- MgOH2 sludge Salt (NaCl) Pretreatment Primary Water Recovery ZLD section

What s new? No pretreatment Crystallizer based on industrial CaCl 2 production Electric Power Recovered Water Steam and/or Electric Power FGD purge CaCl2-MgCl2 Chemistry Brine Concentrator Evaporator Blowdown CoLD TM Crystallizer Centrifuge or Filter Salt CaCl2 & MgCl2 No Pretreatment Primary Water Recovery ZLD section

Requires power and/or steam, no chemicals, reduced sludge COLD TM

Two Options for Evaporation of FGD Wastewater Option 1: Pretreat FGD Wastewater Using Lime-Soda Ash softening Replace Ca and Mg with Na Chemistry is based on NaCl Option 2: Evaporate FGD Wastewater Directly Chemistry is based on CaCl 2 and MgCl 2

At atmospheric pressure, the boiling point curve chases the solubility curve Boiling Point

By lowering the pressure, the boiling point is lowered and a solid phase can form Boiling Point

CoLD TM Process Crystallization of high solubility salts at Low Temperature and Deep Vacuum

What is the CoLD TM Process? A conventional forced circulation crystallizer fitted with a vacuum system Energy for evaporation can be provided by a conventional indirect heat pump, using a refrigerant fluid. Alternately, energy for evaporation can be provided by steam, and low temperature sink can be provided by chilled water. Low operating temperature lowers the solubility of the dissolved salts, so they crystallize at a lower concentration. CoLD TM Process suited for waste streams containing highly soluble salts (e.g. FGD and IGCC blowdown, produced water, landfill leachate) Confidential to HPD

Steam Driven CoLD TM Crystallizer Crystallizer Vapor Body Surface Condenser NCG Vent Chilled Water Crystallizer Heater Recovered Water Feed Recirculation Pump Crystallizer Feed Tank Recovered Water Dewatering Device Solids to Disposal

Indirect Heat Pump CoLD TM Crystallizer

Advantages of New HPD Process No softening required => No chemicals required, no sludge produced. A stable, solid product is produced directly using only electric power. Chemical costs are eliminated and solids disposal costs are greatly reduced. Energy costs are still low. Complexity and footprint of equipment are greatly reduced. Materials of construction can be reduced

Result of CoLD TM Process ZLD

Economic comparison of FGD ZLD Options Facility Comparison ZLD #1: 350 gpm capacity, Softening, Evaporator, Crystallizer ZLD #2: 350 gpm capacity, Evaporator, CoLD TM Crystallizer Economic Comparison ZLD #1 ZLD #2 Cap - Amor $5.4MM $5.4MM O&M $2.8MM $2.8MM Chemicals $6.3MM $250k Disposal $4.5MM $1.0MM Energy $1.8MM $2.3MM Total Opex $15.4MM $6.4MM Net Annual Cost $20.8MM $11.8MM $/gal $0.125 $0.071 NPV savings of $88MM over 15 yrs at 7% discount rate

Thank You Bill Shaw T 815-609-2241 M 414-418-4948 E bill.shaw@veoliawater.com