- lmpurlues ln waLer - Pardness and alkallnlLy - Solublllues - pP and Cycles of concenLrauon - Coollng waLer LreaLmenL ! Corroslon and Scale lnhlblLors ! 8locldes - Cperauon and Lesung General Properties of Water - Some of Lhe properues of waLer whlch make lL ldeal for lndusLrlal coollng processes are llsLed below: ! WaLer has Lhe capaclLy Lo sLore and LransporL heaL ! WaLer absorbs more heaL per pound Lhan any oLher lnorganlc subsLance ! WaLer has Lhe followlng physlcal properues: " Cne pound of waLer glves up 144 81u's upon freezlng " AL aLmospherlc pressure, waLer freezes aL 32 deg l and bolls aL 212 deg l " WaLer ls mosL dense aL 40 deg l " Cne pound of waLer, when Lransformed lnLo sLeam, releases 970 81u's " ure waLer does noL exlsL ln naLure General Properties of Water - 1here are Lwo maln sources of waLer, noLe general dlerences ! Wells and sprlngs are classled as ground waLer sources ! Low suspended sollds and dlssolved oxygen, hlgh dlssolved sollds lncludlng lron, hardness, and alkallnlLy, and also hlgh carbon dloxlde ! 8lvers and lakes are classled as surface waLer sources ! Plgh suspended sollds and dlssolved oxygen, low dlssolved sollds lncludlng lron, hardness, and alkallnlLy, and also low carbon dloxlde Types of Impurities in Water - Suspended sollds ! 1urbldlLy " llnely dlvlded suspended or colloldal mauer (clay, sllL, dlrL, organlc mauer) ! Color " An arblLrary sLandard scale used Lo measure soluble organlc maLerlals ln waLer !"#$%&' Ca Mg k na le, Al, Cu Zn, Sl "&$%&' Cl PCC 3 CC 3 SC 4 C 4 nC 3 Types of Impurities in Water (cont.) - ulssolved sollds ! ulssolved mlneral sollds " When raln falls, lL scrubs Lhe aLmosphere of carbon dloxlde " Carbon dloxlde mlxes wlLh waLer Lo form a weak acld called carbonlc acld " 1he carbonlc acld dlssolves mlneral sollds conLalned ln naLure, such as: ! LlmesLone (calclum carbonaLe), dolomlLe (magneslum carbonaLe), epsom salL (magneslum sulfaLe), gypsum (calclum sulfaLe), sand (slllca), and common salL (sodlum chlorlde). " Mlnerals conLalnlng sodlum have a relauvely hlgh solublllLy ln waLer " Mlnerals conLalnlng calclum and magneslum have a relauvely low solublllLy ln waLer Types of Impurities in Water (cont.) - ulssolved Cases ! Cxygen " Corroslve Lo meLal aL elevaLed concenLrauons " SolublllLy ln waLer depends on LemperaLure, surface area and pressure ! Carbon uloxlde " Wlll form carbonlc acld, a weak acld, when dlssolved ln waLer " Carbonlc acld dlssoclaLes Lo form blcarbonaLe and carbonaLe alkallnlLy whlch ls pP dependenL " SolublllLy ln waLer depends on LemperaLure, surface area and pressure Types of Impurities in Water (cont.) - Mlscellaneous lmpurlues ! 8acLerla LhaL requlre oxygen and produce carbon dloxlde are aeroblc bacLerla ! 8acLerla LhaL do noL requlre oxygen and produce hydrogen sulde are anaeroblc bacLerla ! Algae favors exposure Lo sunllghL ! lungl favors dark secluded areas Hardness and Alkalinity - Pardness (calclum and magneslum) and alkallnlLy (blcarbonaLe and carbonaLe) boLh play a ma[or role ln coollng waLer LreaLmenL: " 1he weak acld, carbonlc acld, LhaL ls formed durlng ralnfall has Lhe ablllLy Lo dlssolve mlnerals ln Lhe earLh's sLraLa " 1he acld soluuon ls composed of hydrogen, Lhe posluvely charged poruon of Lhe soluuon (acldlc poruon), and a negauvely charged counLerparL " lf Lhe earLh's sLraLa conLalns appreclable quanuues of llmesLone and dolomlLe, Lhen Lwo of Lhe prlmary reacuons beLween Lhe weak acld and Lhe sLraLa wlll be wlLh Lhe calclum carbonaLe and magneslum carbonaLe Hardness and Alkalinity (cont.) - Pardness (calclum and magneslum) and alkallnlLy (blcarbonaLe and carbonaLe) boLh play a ma[or role ln coollng waLer LreaLmenL: " As Lhe mlneral dlssolves, boLh Lhe calclum and carbonaLe (as well as Lhe magneslum and carbonaLe), go lnLo soluuon " Cnce dlssolved, boLh Lhe calclum and magneslum (Lhe posluvely charged poruons of Lhe mlneral), Lend Lo favor reverung" back Lo Lhelr naLural lnsoluble sLaLe " When comblned wlLh oLher mlneral lmpurlues, calclum and magneslum wlll preferenually preclplLaLe ouL of soluuon and form an lnsoluble sludge " 1he reacuon of calclum and magneslum ln waLer wlLh soaps and deLergenLs creaLes an undeslrable sludge whlch can make launderlng dlmculL. 1he dlmculLy or hard Lo wash condluon" led Lo Lhe Lhe Lermlnology WaLer Pardness" Solubilities - 1he common mlneral subsLances can be classled lnLo four caLegorles based on solublllLy: ! Calclum and magneslum compounds rules of Lhumb " SolublllLy decreases when LemperaLure rlses, alkallnlLy lncreases, and avallable carbon dloxlde decreases " 8ouom llne: hardness salLs are more llkely Lo drop ouL aL hlgh LemperaLures and pP ! Sodlum compounds rules of Lhumb " SolublllLy lncreases as LemperaLure lncreases. lf deposlLs wlLh sodlum are found, lL can generally be aurlbuLed Lo exLreme concenLrauons or evaporauon Lo dryness " 8ouom llne: Sodlum compounds are rarely a problem caused by waLer LreaLmenL) !"#$%&' Ca Mg k na le, Al, Cu Zn, Sl "&$%&' Cl PCC 3 CC 3 SC 4 C 4 nC 3 Solubilities (cont.) - 1he common mlneral subsLances can be classled lnLo four caLegorles based on solublllLy !"#$%&' : ! Slllca dloxlde rule of Lhumb " SolublllLy lncreases as alkallnlLy lncreases ! lron and manganese compounds rule of Lhumb " SolublllLy decreases as waLer alkallnlLy lncreases and as Lhe degree of oxldauon lncreases (l.e. oxygen, chlorlne, bromlne) !"#$%&' Ca Mg k na le, Al, Cu Zn, Sl "&$%&' Cl PCC 3 CC 3 SC 4 C 4 nC 3 pH and Cycles of Concentration - uened exacLly, pP ls Lhe logarlLhm of Lhe reclprocal of Lhe hydrogen lon concenLrauon ln Lhe reacuon - A more slmple explanauon ls LhaL pP ls a number beLween 0 and 14 LhaL denoLes varlous degrees of acldlLy and alkallnlLy, wlLh neuLral waLer aL pP 7. 8elow 7 becomes lncreaslngly acldlc, whlle above 7 becomes lncreaslngly alkallne pH and Cycles of Concentration (cont.) - pP ls a very lmporLanL parameLer ln waLer LreaLmenL, especlally ln coollng waLer LreaLmenL. As waLer ls cycled, alkallnlLy concenLraLes, so subsequenLly pP lncreases, example: - We call Lhls example as belng 2 cycles of concenLrauon, where mlneral concenLrauons, as well as conducuvlLy, are doubled - AL uMC Shadyslde, Lowers average 3 cycles of concenLrauon WaLer wlLh 100 ppm alkallnlLy WaLer wlLh 200 ppm alkallnlLy, pP lncrease Add heaL, lose x Lhe volume of waLer Lhrough evaporauon Langelier Saturation Index (LSI) - A numerlcal value for Lhe scallng poLenual of calclum carbonaLe (CaCC 3 ) - 1he equauon ls a numerlcal comblnauon of: ! 1oLal dlssolved sollds ! 1emperaLure ! Calclum hardness ! AlkallnlLy ! pP - A posluve LSl ls scale formlng, a negauve LSl ls corroslve, and zero ls perfecL equlllbrlum LSI/RSI Calculation - LSl = pP - pP s - pP s = 9.3 + 1uS[)] + 1emp[)] *!Ca[)] + Alk[)])
Methods of Treatment for High LSI - Acld leed ! 8y reduclng pP ln coollng waLer, Lhe equauon LSl = pP - pP s
means LhaL LSl wlll be reduced, Lherefore calclum carbonaLe scallng poLenual ls reduced ! roper dlluuon of acld ls crlucal Lo conLacL all polnLs of Lhe sysLem. lL ls !"#$%&'(& &$ *+,!# &-* ./.&*" 0!&- .'1*2,'%3. lf acld feed ls losL or lnemclenL Methods of Treatment for High LSI #2 - Crganlc phosphonaLes comblned wlLh polymers can wlLhsLand LSl Lo + 3.0 - usually safe Lo malnLaln LSl aL + 2.3 - AnoLher meLhod of conLrolllng LSl ls soened make-up, buL requlres manhours for regenerauon and malnLenance Cooling Water Treatment - Cb[ecuve of a coollng waLer LreaLmenL program: ! MalnLaln opumum heaL Lransfer ln process equlpmenL and heaL exchangers ! lnsure equlpmenL rellablllLy and avallablllLy ! Mlnlmlze operaung cosLs ! rovlde predlcuve LreaLmenL recommendauons for sysLem operaung changes and Lower conLamlnauon ! MalnLaln healLhy envlronmenL ln molsL areas around perlmeLer of Lower ! Assure sysLem clrculauon Lo keep all areas wlLh fresh ow on a regular basls Cooling Water Treatment (cont.) - Ma[or concern areas: ! Scale: lormauon of lnsoluble deposlLs on heaL Lransfer surfaces, usually hardness salLs on Lhe mosL crlucal (or houesL) areas " Plgh poLenual wlLh hlgh LemperaLures, hlgh pP, excesslve alkallnlLy, hlgh dlssolved sollds, and hlgh hardness ! Corroslon: Loss of meLal by reacuon wlLh Lhe envlronmenL " lormauon aL Lhe anode or caLhode semng up an elecLrlcal clrculL", or oxldauon of base meLal ! loullng: Mlcroblologlcal and suspended sollds deposluon " Algae, fungl, or bacLerla dependlng upon locauon ln sysLem, can acL as Lhe glue LhaL holds deposlLs LogeLher" Changing Chemistries Over the Years - 1oxlc naLure of ChromaLe - ueslre Lo LllmlnaLe Acld - ueslre Lo CperaLe aL Plgh Cycles - Lconomlc ressure - More Lecuve lnhlblLors Overview - Carbon SLeel Corroslon rocess - Pow Chemlcal 1reaLmenLs Work - 1reaLmenL rograms: +,- ./0% 12 3-/40 - 1he luLure Corrosion Process AnCuL le -le +2 + 2e -
CA1PCuL P 2 C + xC 2 + 2e - - 2CP - Rust Formation le +2 hydraLed Lo le(CP) 2
le(CP) 2 oxldlzed Lo le(CP) 3 le(CP) 3 preclplLaLes
Anodic Inhibitors lnhlblL oxldauon of lron romoLe gamma - le 2 C 3 reclplLaLes ll volds
High Calcite Saturation: 240X (LSI=2.8) $)*+,+-./0 B $)*+)+2.) 861234 C.0674 97:;< 20 mg/L 30 mg/L L 91 100 81C 72 76 PLu 38 33 AM - 31 PA 44 MA 46 39 MA 31 olyasparuc Acld - 39 Green Chemistry Low/non-Zlnc Low/non-hosphaLe MA
Conclusion - MosL lmporLanL uevelopmenL: lmproved olymers - olymer of Cholce: 60/40 AA/AMS - 8esL Plgh CalclLe SaLurauon lnhlblLor: naLcolene L - luLure: More SLudles needed for Creen ChemlsLrles Oxidizing Biocides - Chlorlne based ! noL as eecuve above pP 7.3 " Sodlum hypochlorlLe ! 8leach" avallable aL 14 " P1P ! Calclum hypochlorlLe powder, rapld dlssolvlng " Chlorlne lsocyanuraLe LableLs ! Crganlc chlorlne rapld dlssolvlng LableLs " Chlorlne dloxlde ! Comblnauon of sulfurlc acld and hypochlorlLe Oxidizing Biocides (cont.) - 8romlne based ! Lecuve above pP 7.3 " SLablllzed bromlne ! 14 bromlne comblned wlLh sodlum hypochlorlLe " 8romlne hydanLoln LableLs ! Slow dlssolvlng fed vla bromlnaLor " 8romlne lsocyanuraLe ! 8apld dlssolvlng bromlne LableLs Non-Oxidizing Biocides - Llquld blocldes used Lo supplemenL an oxldlzlng bloclde program ! led vla pumps on 7 day umer ! AcLs as a polson Lo klll bacLerla/algae/fungl/mold " WSC (142L) - algae, bacLerla, fungl " CarbamaLe - bacLerla, sulfaLe reducers, fungl " M81 -bacLerla, sulfaLe reducers, fungl " 1erbuLhylazlne - algae " lsoLhlazollne - bacLerla, sulfaLe reducers, fungl " u8nA - bacLerla " CluLaraldehyde - bacLerla, sulfaLe reducers, fungl " 1hlone - bacLerla, fungl " 1rlazlne - algae " uCP - bacLerla, sulfaLe reducers, fungl Operation and Testing - MolybdaLe 1esL 1. Add 1.3 mL of Lower waLer Lo each vlewlng Lube 2. Add Lap waLer Lo 1sL mark of each vlewlng Lube (3 mL mark) 3. Add one Molybdenum 1 8eagenL owder lllow Lo one of Lhe Lubes 4. Add elghL drops of Molybdenum 2 8eagenL Lo Lhe same Lube used ln SLep 3 3. lnserL Lhe Lube from SLep 4 lnLo Lhe rlghL openlng of Lhe color comparaLor 6. lace Lhe blank lnLo Lhe le openlng, and hold up Lo naLural llghL 7. 1he conLrol dlsplay range ls 1.1 mg/L Lo 1.8 mg/L Operation and Testing (cont.) - 1oLal and lree Palogen 1esL 1. llll a vlewlng Lube Lo Lhe rsL llne (3 mL) wlLh sample waLer 2. Add elLher LoLal or free chlorlne powder plllow Lo Lhe sample 3. lor LoLal chlorlne LesL, allow 3 mlnuLe reacuon ume before readlng resulL 4. vlew sample ln comparaLor, conLrol free chlorlne 0.1 -0.3 mg/L and LoLal chlorlne < 1.0 mg/L. - ConducuvlLy ! ConLrol 1600 -2000 umhos conducuvlLy - Sanlcheck 1esL klL ! ConLrol < 10 3 bacLerla/mL Review Quiz - WhaL ls Lhe scale LhaL we are mosL concerned wlLh ln reclrculaung coollng waLer sysLems? - lf Lhe makeup waLer ls 400 conducuvlLy, and Lhe Lower waLer ls aL 2000 conducuvlLy, whaL are Lhe cycles of concenLrauon? - WhaL are ways Lo conLrol leglonella bacLerla ln a coollng Lower? - Where ls hardness mosL llkely Lo drop ouL of Lhe waLer soluuon ln a coollng waLer sysLem? - WhaL safeLy equlpmenL ls necessary when handllng LreaLmenL chemlcals?