Reduction of Water Demand in Cooling Towers Dr Paul Hirst Agenda •Cooling Tower Basics – Water Losses – Cycles of Concentration •Limitations on Cycles – Chemical – Hydraulic – Dynamic Cooling Tower System Evaporation Heat Load Makeup Blowdown Cooling Tower Recirculating Pump Cooling Tower Water Losses •Evaporative Water Losses •Non Evaporative Water losses Evaporative Water Losses •Water that is evaporated from the cooling tower (does not carry solids) E (m3/hr) Where: = RR x Cp x T x Ef / 556 RR is the Recirculation Rate in m3/hr Cp is the Specific Heat Capacity (1 kcal/kg/oC) T is the Temperature Change in oC Ef is evaporation factor and depends on Wet bulb temperature, Relative Humidity 556 = kcal/kg to evaporate water Non Evaporative Water Losses •Drift - The water lost from the tower as entrained droplets in the exhaust air •Windage - The water lost from the tower as a result of wind action •Blowdown - The water deliberately purged from the system to control water chemistry Total Non Evaporative Water Losses •All water that is lost from the cooling system (carries solids) – Controlled Losses • Blowdown – Uncontrolled losses • drift & windage • leaks • side stream filter backwashes • sample coolers Makeup Water •The water added to replace water lost from the cooling system: > Evaporation > Total Non Evaporative Water Losses MU = E + BD Cooling Tower Cycles of Concentration Cycles of Concentration (Cycles) •The dissolved solids concentration in the blowdown relative to the makeup – 5 cycles – BD has 5x concentration of MU – 12 cycles – BD has 12x concentration of MU •A measure of how efficiently the water is used – Evaporation fixed by heat load & climate – Non evaporative losses controlled by cycles – Increased cycles = reduced losses MU (m3/hr) Effect of Tower Cycles on Makeup and Blowdown 800 700 600 500 400 300 200 100 0 RR = 20,000 m3/hr T = 9 oC MU BD 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Cycles Limitations on Cycles •Chemical •Hydraulic •Dynamic Corrosion Deposition Particle Entrapment Growth Sites Biofouling Effect of Cycles on Corrosion Factors Affecting Corrosion •Conductivity •Acidic Anions e.g. Sulphate & Chlorides •Materials of Construction – Chlorides with Stainless Steel – Sulphates with Concrete Effect of Conductivity Classic Corrosion Cell WATER (ELECTROLYTE) Fe 2+ O 2 ANODIC REACTIONS Chemical Oxidation Fe2+ 2 CATHODE ELECTRON FLOW CATHODIC REACTIONS Chemical Reduction In Neutral or Alkaline Water, This is the Cooling Water Reaction: + 2e- 2Fe(OH)2 + 1/2O2 + H2O O O- Fe(OH)3 Fe(OH)2 ANODE Fe0 OH H2 O - 2Fe(OH)3 1/2O2 + H2O + 2e- - 2OH In Acid Media: 2H+ + 2e1/2O2 + 2H+ H2 (HYDROGEN EVOLUTION) + 2e- H2O Factors Affecting CorrosionConductivity Effect of Acidic Anions Crevice Corrosion - Initial Stage O2 OH- Cl- e- O2 O2 Na+ e- M+ Na+ Cl- O2 Na+ O2 M+ OH- Cl- e- Na+ O2 M+ OH- e- M+ M+ OH- e- Crevice Corrosion - Later Stage Na+ O2 OH- O2 OH- ee- Cl- O2 O2 Na+ M+ Cl- M+ Cl- Cl- ClCl- O2 O2 M+ OH- OH- H+ OH- e- Cl- M+ H+ ClH+ Cl- M+ H+ Cl- O2 M+ M+ M+ ClM+ M+ M+ H+ ClM+ Cl- Crevice Corrosion Tube Plate Attack at Gasket Crevice Corrosion - Coupons Effect of Materials of Construction Critical Pitting Temperature 304 CPT Chloride Limits o •40 C – 400 ppm •50 oC – 200 ppm •60 oC – 150 ppm 316 CPT Chloride Limits o •40 C – 4000 ppm •50 oC – 1500 ppm •60 oC – 800 ppm Note: These are guidelines for a clean system Stress Corrosion Cracking - SS + Cl Sulphate Attack on Concrete Attack on Concrete by Soils & Waters Containing Sulphate 1 Relative Degree of Sulphate Attack Percent Water-Soluble Sulphate (as SO4) in Soil Samples ppm Sulphate (as SO4) in Water Samples Negligible 0.00 to 0.10 0 to 150 Positive1 0.10 to 0.20 150 to 1000 Considerable2 0.20 to 0.50 1000 to 2000 Severe2 Over 0.50 Over 2000 Use Type II cement 2 Use Type V cement Effect of Cycles on Deposition Types of Deposition •Scaling – Mineral Scale – Increased risk with increased cycles •Fouling (see later) – Suspended Matter – Corrosion Products – Biological Scaling Common Scales •Calcium Carbonate CaCO3 •Calcium Sulfate CaSO4 •Calcium Phosphate Ca3(PO4)2 •Magnesium Silicate MgSiO3 •Aluminium Silicate Al2O3.SiO2 •Zinc Phosphate Zn3(PO4)2 •Iron Phosphate FePO4 •Calcium Magnesium Silicate CaO.MgO.2(SiO2) •Silica SiO2 Factors Affecting Scale Formation •Scale forms when solubility is exceeded •Rate depends on degree of super saturation – Concentration of Ions – Temperature, most salts increase in solubility with increasing temperature except for Ca and Mg Salts – pH/Alkalinity, most salts decrease in solubility with increasing alkalinity/pH except for Silica – Oxidation State, Fe and Mn salts increase in solubility with decreasing oxidation state Calcium Carbonate Solubility 1000 45 C Calcium, ppm CaCO3 900 800 700 60 C 50 C Scaling (Supersaturated) 600 500 400 300 200 Non Scaling (Unsaturated) 100 0 150 250 350 450 Alkalinity, ppm CaCO3 @ 4000 mmhos 550 650 Calcium Phosphate Solubility 600 Scaling (Supersaturated) 500 Calcium ppm CaCO3 400 pH = 7.0 300 200 pH = 8.2 100 Non Scaling (Unsaturated) 0 2 4 6 Orthophosphate ppm PO4 8 10 Indices & Guidelines Commonly Used Indices CaCO3: – Langelier Saturation Index (LSI) – Ryznar Stability Index (RSI) – Stiff-Davis Stability Index (S&DI) • High Conductivity Waters > 10,000 ppm TDS •Calculated Using: – Several charts, nomograms & formulae – Some give quite varied answers! Langelier Saturation Index LSI = pHa - pHs Where: – pHa = Actual pH – pHs = Saturation pH – pHs is a function of Ca, M-Alk, TDS, and Temperature Guidelines: – Positive (+) = scale is likely to form – Negative (-) = scale is not likely to form Simple Modelling GEWater &ProcessTechnologies Acme VOL TOWER WATER CYCLING ANALYSIS ANZ RR 1,500 (m3/hr) DT 10 (deg C) EVAP 27 (m3/hr) ( VERSION 8.0 Metric ) o 60 C (Hotest Skin) o 50 C (Bulk Water) Cooling Description 0.9 M-ALK FACTOR CYCLES pH M-ALK 30/04/2007 Ca Mg SiO2 COND Cl SO4 MgSi CMSi RT75 (day) 7.80 100 60 2.0 8.23 180 3.0 8.55 270 4.0 8.78 5.0 (m3) 1.00 F LSI 300 B.D. M.U. (m3/hr) (m3/hr) 40 25 500 50 120 80 50 1000 100 40 0.38 ok ok 0.01 27 54 180 120 75 1500 150 60 1.03 ok ok 0.02 14 41 360 240 160 100 2000 200 80 1.49 ok ok 0.03 9 36 8.96 450 300 200 125 2500 250 100 1.85 ok ***** 0.04 7 34 6.0 9.11 540 360 240 150 3000 300 120 2.14 ok ***** 0.05 5 32 7.0 9.23 630 420 280 175 3500 350 140 2.39 ok ***** 0.06 5 32 8.0 9.0 9.34 9.43 720 810 480 540 320 200 360 ***** 4000 4500 400 450 160 180 ***** ***** ***** ***** ***** ***** 0.07 0.09 4 3 31 30 10.0 9.52 900 600 400 ***** 5000 500 200 ***** ***** ***** 0.10 3 30 11.0 9.59 990 660 440 ***** 5500 550 220 ***** ***** ***** 0.11 3 30 12.0 9.66 1080 720 480 ***** 6000 600 240 ***** ***** ***** 0.12 2 29 13.0 9.73 1170 780 520 ***** 6500 650 260 ***** ***** ***** 0.13 2 29 14.0 9.78 1260 840 560 ***** 7000 700 280 ***** ***** ***** 0.14 2 29 15.0 9.84 1350 900 600 ***** 7500 750 300 ***** ***** ***** 0.15 2 29 16.0 9.89 17.0 9.94 23.0 10.18 1440 1530 2070 960 1020 1380 640 ***** 680 ***** 920 ***** 8000 8500 11500 800 850 1150 320 340 460 ***** ***** ***** ***** ***** ***** ***** ***** ***** 0.16 0.17 0.24 2 2 1 29 29 28 29.0 10.37 2610 1740 1160 ***** 14500 1450 580 ***** ***** ***** 0.30 1 28 MAKEUP 20 -0.56 Advanced Modelling Cooling Tower Simulation Calcite supersaturation Vs. pH and Cycles of Concentration @ 140F S( C aC O3) w it h T e m p =140. an d 0. p p m o f UNT REA T ED Untreated 30 25 20 S( CaCO3) 15 10 5 0 8 4 3 .8 7.8 3 .6 3 .4 Cy c les 7.6 3 .2 3 2 .8 7.4 2 .6 7.2 2 .4 2 .2 2 7 pH Cooling Tower Simulation Calcite supersaturation Vs. pH and Cycles of Concentration @ 140F S( C aC O3) w it h T e m p =140. an d 2. p p m o f A EC Treated 30 25 20 S( CaCO3) 15 10 5 0 8 4 3 .8 7.8 3 .6 3 .4 Cy c les 7.6 3 .2 3 2 .8 7.4 2 .6 7.2 2 .4 2 .2 2 7 pH Hydraulic Limitations Hydraulic Limit on Cycles •All systems have uncontrolled losses (e.g. leaks, drift, windage) •When: Uncontrolled Losses > Blowdown Required to Control Water Chemistry •Then: Actual Cycles < Target Cycles •Cycles no longer limited by chemical constraints, said to be hydraulically limited Hydraulic Limit on Cycles •Hydraulic limit on cycles can be determined: – Measure “Total Non Evaporative Water Losses” • Decay study using MoO4, LiCl – Measure “Controlled Losses” (blowdown) • Flow meter, Rotameter – Calculate “Uncontrolled Losses” (difference) – Calculate Hydraulic Limit from Uncontrolled Losses •Need to reduce Uncontrolled Losses to further increase cycles beyond Hydraulic Limit System Dynamics Concentration (ppm) Retention Time (a.k.a. Half life or HTI) 80 70 60 50 40 30 20 10 0 RT50 RT75 t1/2 1 t1/2 2 3 4 5 Time (Days) 6 7 Calculating System Half Life Half Life t1/2 = Ln 2 x System Volume / System Losses Note Ln 2 = 0.693 Retention Time – RT50 = t1/2 – RT75 = 2 x t1/2 Impact of Half Life •Typical half life for industrial cooling tower – 2-4 days design – 5-7 days actual •Long half life can cause: – Degradation of treatment chemicals – Persistence of upset conditions • Wind Blown Solids • Process Contamination Copper Corrosion Inhibitors Adsorbed Azole Layer Az Az Az ++ Cu Az Azole Molecules Copper Ions ++Az Cu Az Az Az Azole Thin Film Az Az Az Az Az Az Az Az Az Az Az Az Az Az Az Az Az Az Copper or Copper Alloy Metal Surface Galvanic Plating of Copper onto Steel MS and Copper Corrosion - TTA 4 .0 T T A /M S 3 .5 C o rro s io n R a te ( m p y) T T A /C u 3 .0 2 .5 C h lo rin a tio n S ta rts 2 .0 1 .5 1 .0 0 .5 0 .0 0 20 40 60 80 T im e (h r) 100 120 140 Copper Corrosion Test - HRA 4 .0 TTA C o rro s io n R a te ( m p y) 3 .5 HRA BZT 3 .0 2 .5 2 .0 Add 5 ppm N aO C l 1 .5 1 .0 0 .5 0 .0 0 5 10 15 20 T im e (h rs ) 25 30 35 40 MS and Copper Corrosion - HRA 4 .0 3 .5 H R A /M S C o rro s io n R a te (m p y) H R A /C u 3 .0 2 .5 2 .0 C h lo rin a tio n S ta rts 1 .5 1 .0 0 .5 0 .0 0 20 40 60 80 T im e (h r) 100 120 140 CaCO3 Scale Inhibitors AEC – Chlorine Resistance 1 1 0 7 p p m C a ; p H 8 .6 ; T e m p 7 0 C 100 AEC % In h ib itio n 90 HEDP 80 70 60 50 0 2 5 F re e C h lo rin e , p p m 10 Dispersants Fouling •Sources > Suspended Solids in makeup or wind blown > Corrosion Products generated in the system > Organic materials and microorganisms can act as binding agents •Settle in low flow areas (obey Stokes Law) – Shell & Tube exchangers with water on shellside – Plate & Frame exchangers Dispersants •Dispersants control particle size by interfering with agglomeration •Adsorb on particle surfaces imparting excess -ve charge Repulsion Polyacrylic Acid (PAA) CH2 CH C - O O x •Effective dispersants for silt and clays •NOT Effective for > High levels (>1 ppm) of iron or manganese > calcium phosphate Polyacrylamide CH2 CH C NH2 O x •Long retention times and/or high temperatures > Break down (hydrolyzes) to Acrylic Acid > NH3 liberated •When it hydrolyzes it is just like PAA AA/AMPS Copolymer of Acrylic Acid and 2-Acrylamido-2-Methylpropyl Sulfonic Acid; AA/AMPS HPS-I Polymer (C – C)x (C – C)y C ONa O CH2 ETHER O LINKAGE CH2 CH OH CH2 SO3Na Robust ether linkage does not hydrolyse allowing longer retention times (higher cycles) Treating Long Retention Time Systems Treating Long Retention Time Systems (a.k.a. Running at High Cycles) •The GE Approach > Use continuous chlorination at 0.5-1.0 ppm for Legionella control (CTI best practice) > Use halogen stable treatment chemistries •The Alternative Approaches > Overdose products to compensate – Costly – Beware misleading monitoring and control data! > Use non oxidising biocides or weak (stabilised) oxidising biocides – Beware Legionella! Questions?