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Cooling Water WaterCycle

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1. UNTREATED Chooset he Treated or Untreated color coding optionf rom theO ptions Pop upM enu Calcite Saturation Level 350 300 250 200 150 100 50 Saturation Level QQ 7 1e 3114044 3 ONYvu ONIL H3dO French Creek Softwar Treated vs Untreated Profile Examples The BLUE color code indicates a safe zone for operation TREATED WITH HEDP 52 Wate rCycl e R Calcite Saturation Level helps you choose the optimum treatment amp identifies inhibitor upper limits the problem extreme scale potential Saturation Level sajo o 00 8 00 6 3 ldHOHd ADNVY DNILY UNTREATED solution options HEDP PLUS PAA Dosage Profile HEDP PLUS PMA Dosage Profile PBTC PLUS COPOLYMER Dosage Profile An HEDP PAA combination The HEDP PMA combination The PBTC PMA combination is functional over a limited expands the effective provides the broadest portion of the desired operating range operating range operating range significantly U 160 60 0 a 140 50 0 60 0 P 120 40 0 50 0 90 LI go 100 40 0 E p 80 2 30 0 8 o js 20 0 30 0 2 M 100 20 0 2 20 10 0 9 0 0 YELLOW color coding o o o indi RED color coding 8 indicates operation g qu O i o at the upper end m o indicates operation 8 w of 9 A p ok beyond inhibitor limits 9 of 26 of inhibitor effectiveness va gio NN fo
2. 40 pH PREDICTION Predicting pH as the water cycles is one of the more difficult aspects of computer modeling WaterCycle provides three options chosen from the SELECT PARAMETERS menu form e The DEFAULT curve is a pH Alkalinity curve which is used by several of the major water treatment companies for predicting pH from alkalinity e The USER DEFINED curve uses data input in the INPUT pH ALKALINITY module to predict pH from alkalinity e The Caplan curve is similar to the default curve It is derived from a paper published by Gary Caplan at Corrosion 90 NACE e The Translate Source Water option is based upon a modified Lawrence Caldwell method more commonly applied to pH prediction of softened or mixed waters Report Options Choosing What Output Windows To Display and When Several options are available for displaying and printing table and graphs from WaterCycle The output windows which will display can be selected from the Choose Once Through Windows To Display and Choose Cooling Tower Windows To Display modules in the Preferences menu See the Getting Started section of the manual for an example Choosing What Scale Indices and Ions To Display A report can become cluttered and information sometimes overlooked in an extremely detailed report WaterCycle options allow you to choose the ions to include in reports copied to the Windows Clipboard or printed WaterCycle options also allow you to choose the indicators of scale to
3. Y Ta the treatment is a borderline the treatment will fail af ariy doen choice in this range French Creek Software Inc Kimberton amp Hares Hill Roads Box 684 Kimberton PA 19442 U S A telephone 610 935 8337 http www frenchcreeksoftware com facsimile 610 935 1008 WaterCycle R identifies and solves even the most difficult deposit mg l problems the problems Saturation Level Magnesium Silicate Saturation 40 0 30 0 20 0 10 0 0 0 w qo 7 87 m o M m Q ON N 8 00 8 00 7 00 6 00 5 00 4 00 3 00 2 00 1 00 0 00 Mg SiO2 Inhibitor Dosage Profile Se oAo O 9 8 077 1e 311404d 9SNLLVHZdO 8 40 Saturation Level 1 60 1 40 1 20 1 00 0 80 0 60 0 40 2 N o o O 9 802 2 1e Ams Odd 9NILLVH dO lt the solution Silica Saturation Level Q io T o Ir i0 Q y 8 27 8 13 8 00 7 87 7 73 7 60 00 French Creek Software Inc Kimberton Hares Hill Roads Box 684 Kimberton PA 19442 US A telephone 610 935 8337 http www frenchcreeksoftware com facsimile 610 935 1008 5 O 9 802 2 1e F11404d 39NYH DNILYYSIHO DEVELOPING AND USING INHIBITOR MODELS SELECTING A PRODUCT INPUTTING A FORMULATION DOSAGE MODULATION DEVELOPING INHIBITOR MODELS 53 54 SELECTING A PRODUCT Wa
4. LOGE Lirnit Limit Variable 1 JHydroxyapatite x Sat E os 3900 99 00 Vaiabe 2 po s 5 99 00 qs colo J 9900 4 ss ns en Ts wes o S ipfo Ts oll uuu um uc ETE En Cancel OK After this preliminary data is entered and the Correlate button is pressed to signify completion the module accepts input of water analysis data through almost the same analytical input form that is used in the Once Through Source Analysis module and Cooling Tower Make up Analysis modules The Input Lab Data form adds two 2 significant fields to the water analysis forms dosage and time The input form differs in another way operation The Lab Data Input Form replaces itself with a fresh form every time OK is pressed 63 Water Chemistry Input Sample Date 12 16 1999 E Time 17 54 ine Report Date 12 16 1399 REC 1 Laboratory Test Run Ca PO4 Inhibitor Sample Description Calcium 200 00 Aluminum 0 00 Hydrogen sulfide 0 00 as Ca as Al as H2S Magnesium 0 00 Boron 0 00 Silica 0 00 Mg as as SiO2 Sodium 0 00 Chloride 0 00 Phosphate 3 00 as as CI as PO4 PREVIOUS Potassium 0 00 Sulfate 0 00 Fluoride 0 00 as CaCO3 as 504 as Iron 0 00 Alkalinity 20000 Nitrate 0 00 as CaCO3 as CaCO3 Ammonia 0 00 P Alkalinity 0 00 Temperature 35 00 Activate as NH3 as CaCO3 as C H 7 800 Induction time 382 18
5. Dosaae 3 00 E sec mqiL Corrosionrate 10 00 Fitting Index 0 00 Comment Correlate mpy Change Units Display Result Print Result Recalculate Cancel The Next Page and Last Page buttons allow you to browse through the analysis that have been input and make changes The program will sound a warning when the first analysis on file is reached The program will ask if you wish to add another analysis when the last analysis is reached Once all data has been entered press Correlate to invoke the statistical analysis of the data and generation of an inhibitor file A table of predicted versus input dosages will be displayed Use this table to determine crudely how well the data was modeled A correlation coefficient is also output Typical coefficients for usable models will range from 0 9 to 1 00 Pressing the Graph button will present further information on the correlation in graphical format 64 Predicted vs Actual Dosages vs Calcium PO4 x Sat hh m E r 3 HH a 1 a N j 1 7 7 Wt in T 1 T 1 20 0 40 0 100K 150K Actual Dosage marl Calcium 4 Sat Error vs Temperature 2 Error vs pH 400 400 u 5 3 2 200 2 200 a a E z 0 50 0 60 0 70 0 Temperature pH The Input Lab Data module is available only in the WaterCycle Rx Laboratory Edition The Edit Coefficients module is used to add special rules and safety
6. and their percentages This information is used in conjunction with mathematical inhibitor model coefficients to calculate dosage recommendations The Salesman Edition can use the information in the files but is not capable of displaying this sometimes proprietary information The active 19 ingredient list and their percentages cannot be obtained by loading a product PRD file into the Salesman Edition program WaterCycle Rx Product Manager Edition Files The Product Manager Edition creates the same files that are created by the original WaterCycle program Additionally the Product Manager Edition can create product PRD files It can also access inhibitor INH files The Product Manager Edition can create modify and display product information files PRD The INPUT FORMULATION module is used to access or create a PRD file Active ingredients information is added to the PRD files through the loading of the inhibitor file for the active ingredient being added The appropriate percentage s for active ingredients thus loaded are entered into the form The inhibitor INH files contain the mathematical inhibitor model coefficients to calculate dosage recommendations The Product Manager Edition can use the information in the INH files but is not capable of displaying this sometimes proprietary information or the laboratory data which was used to generate the inhibitor correlations The Product Manager Edition has full access to
7. cooling system Systems have been scaled with silica because the water treater in charge evaluated scale potential at the highest temperature in the system the temperature most conducive to fouling for most compounds Overlooking the solubility profile of silica versus temperature resulted in a scaled condenser inlet area while the outlet area remained clean Evaluating the scale potential for common scalants at both the lowest and highest temperatures anticipated and at the lowest and highest pH values expected could have foretold the impending scale and kept the condenser clean WaterCycle was developed to allow a water treater to readily evaluate the scale potential for common scalants over the broadest of operating ranges without the necessity for tedious manual calculations for the Langelier saturation index Ryznar stability index Puckorius equilibrium index and tricalcium phosphate saturation level Even when all of these common indices are available conflicting results can cloud interpretation of what they are foretelling WaterCycle provides additional information in the form of indicators of scale and corrosion potential which are useful and would be popular if they weren t so difficult to calculate with a pencil paper tables and a calculator WaterCycle allows a water treater to review popular and some less known indicators relatively painlessly to develop a more complete picture of problems and potential problems confronting a c
8. degree of supersaturation acceptable for a system varies with parameters such as residence time the order of the scale reaction and the amount of solid phase scale present in the system To be on the safe side it is recommended that an appropriate inhibitor be fed to a cooling system if the saturation level is above 1 0 The acceptable degree of saturation for a given system should be based upon your experience The author has found the following guidelines useful Calcium carbonate In once through cooling systems treatment is necessary when the saturation level at the highest temperature and pH in the system is above 1 2 to 1 5 A slightly higher degree of supersaturation can be carried in some cooling towers 12 Calcium sulfate Treatment is recommended when the saturation level for gypsum exceeds 1 0 In higher temperature systems gt gt 130 F treatment is required normally when anhydrite saturation level exceeds 1 0 Silica Most cooling waters can carry a silica saturation level of 1 1 to 1 2 WaterCycle silica saturation levels are calculated using the solubility product for amorphous silica A saturation level in this range equates to a cooling water silica level of around 150 ppm as SiOz at an acid to neutral pH and 180 ppm or above in waters with a pH above 8 0 This is comparable to the old guidelines for acid chromate programs 150 ppm as 5102 used by most water treatment companies when such treatments were acc
9. factors to the inhibitor files The raw laboratory analysis and calculated values are stored in a COR file The data is used to create an inhibitor INH file OPERATION HINTS Enter inhibitor dosages on a 100 ACTIVE BASIS Make backup copies of COR files under another name This will prevent anguish and stressed tempers when a COR file with a thousand or so analysis is over written unintentionally 3 Always press Graph after completing the correlation to see the graphs of predicted versus observed dosages and graphs of error 96 versus versus the independent parameters 4 The Options Menu Bar allows correlation graphs to be saved as a PCX TIF or BMP file 5 Always enter at least 5 valid analysis Ne 65 DEVELOPING LABORATORY DATA A common question from WaterCycle Rx users is What should I use for an experimental design French Creek Software recommends that the experimental designs for developing mathematical models for inhibitors include FIVE TEMPERATURES PREFERRED Data should be run at a minimum of three temperatures to account for variation in dosage due to the effect of temperature on reaction rate When possible an experimental design should include five temperatures The temperature range studied should include the lowest and highest temperatures expected in the field or where the models generated by WaterCycle Rx THREE TO FIVE pH POINTS PREFERRED Data should be run at a minimum of three different pH to a
10. from in house laboratory and or field data or obtained from raw material suppliers who use the WaterCycle Rx series as a technical support tool The ENCRYPTION option allows product files to be encrypted as a precaution against prying 57 DOSAGE MODULATION The section describes the basis for the models used by and developed using WaterCycle Rx Models are discussed by parameter DRIVING FORCE The basic parameter to which scale inhibitor dosages have been correlated historically is the driving force for crystal formation and crystal growth Early models attempted to develop models based upon the Langelier Saturation Index or the Ryznar Stability Index More recently correlations have been published to the Practical Stability Index on the back of the Puckorius and Associates slide rule Most water treaters are in agreement that dosage requirements increase with the driving force for scale formation They differ in which driving force is used Calcite saturation level provides an excellent driving force for calcium carbonate scale inhibitor models gypsum saturation level for calcium sulfate in the cooling water temperature range and tricalcium phosphate saturation level for calcium phosphate scale prevention The Momentary Excess indices can also be used effectively to model dosage requirements WaterCycle Rx allows the water treatment chemist to develop models using any of the indices calculated by WaterCycle TIME A second critical fac
11. include in reports copied to the Windows Clipboard or printed Reports can be customized for example to exclude all Momentary Excess indices Refer to the Getting Started section for examples of the forms Choose Ions To Print and Choose Scales To Print These may be accessed from the Preferences Menu Change Range New Product Options In early versions of WaterCycle changing products and displaying the new results could be a cumbersome and sometimes inefficient process You had to leave a graph or table access the Select Parameters form and then go back to the output form or graph to see the results of the change Version 3 0 adds the ability to change the range for a report and see the results updated on the screen without leaving the graph or report For pH profiles you can press the Change Range button on the output form and input a new pH range For Temperature profiles you can press the Change Range button on the output form and input a new Temperature range The New Product and Change Product buttons allow you to select a new treatment and view the new dosages and color coded ranges on the screen 41 The NEW TREATMENT and CHANGE RANGE selections on output windows allows you to quickly see the impact of parameter or treatment changes RECIRCULATING WATER CHEMISTRY Sample ID 0 Report Date 12 16 1999 Sampled 12 16 1999 at 1312 CONCENTRATION RATIO CATIONS 1 00 1 50 2 00 2 50 2 00 2 50 4 00 Calcium as Ca 111 00 166 50
12. kinetic model 12 The index does not account for two critical factors The pH will change in some cases as precipitate forms by the precipitation of alkalinity contributors such as carbonate or phosphate Secondly the index does not account for changes in driving force as the reactant levels decrease due to precipitation WaterCycle includes Momentary Excess precipitation to equilibrium as a final indicator of scale potential for the scalants covered by the computer program WaterCycle expresses the precipitation to equilibrium in parts per million Momentary Excess does not represent a quantitative assessment of the amount of a fouling which will precipitate It is an indicator of the capacity of a water to scale and can be compared 11 to the buffer capacity of a water The calculation method is covered in more detail in the literature 12 INTERPRETING WaterCycle INDICES Scale Potential As Indicated By Saturation Level All but one of the indices discussed in this section describe the tendency of a water to form or dissolve a particular scale These indices are derived from the concept of saturation For example saturation level for any of the scalants discussed is described as the ratio of a compounds observed ion activity product IAP to the ion activity product expected if the water were at equilibrium Ksp In WaterCycle graphically profiles the degree of supersaturation is labeled as this ratio IAP Ksp This ratio has many nam
13. the System into any updated or derivative work without the prior written consent of French Creek For purposes of this Agreement the term updated or derivative work is intended to refer to the use of the System either in whole or in part in the development of some other system of work whether or not such other system or work is operated by computer or otherwise The term updated or derivative work is not intended to refer to any interfaces or other methods of access to the System 5 WARRANTY For a period of thirty days following Customer s receipt of the System French Creek warrants that Customer shall have the right to return the System and to receive a full refund of related license and initial maintenance fees exclusive of travel living and out of pocket expenses if the System fails to operate substantially in accordance with the System documentation EXCEPT AS OTHERWISE STATED HEREIN FRENCH CREEK MAKES NO REPRESENTATION OR WARRANTY EXPRESS IMPLIED OR STATUTORY CONCERNING THE SYSTEM OR SERVICES PROVIDED HEREUNDER FRENCH CREEK SPECIFICALLY DISCLAIMS ANY EXPRESS OR IMPLIED WARRANTY OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE FOR SUCH SYSTEM OR SERVICE CUSTOMER UNDERSTANDS AND AGREES THAT THE SYSTEM IS LICENSED STRICTLY ON AN AS IS BASIS The terms and conditions of this section shall survive any termination of this Agreement 6 INDEMNITY French Creek warrants that it has all necessary rights to license th
14. the formulation information such as active ingredients and their percentages WaterCycle Rx Laboratory Edition Files The Laboratory Edition creates the same files that are created by the original WaterCycle program The Laboratory Edition has all of the capabilities of the Product Manager Edition It can create product PRD files Additionally the Laboratory Edition can be used to directly edit inhibitor INH files The Laboratory Edition has the unique capability of processing COR file data to generate inhibitor INH files The Laboratory Edition can create modify and display product information files PRD The Laboratory Edition has full access to INH files including the capability of displaying the sometimes proprietary information stored in them The Laboratory Edition has full access to laboratory and field data stored in COR files COR files contain water chemistry information dosage required for 100 inhibition and temperature data for laboratory and or field data A series of analysis can be used to statistically model the inhibitor performance and develop a INH file mathematical model A minimum of five 5 analysis are required for a COR file to be used 20 GETTING STARTED System Requirements Installation Selecting Analytical Units Carbonate Calculations 21 22 System Requirements As a general rule French Creek Software programs will run on the minimum system configuration for a given Windows o
15. 222 00 277 50 222 00 388 50 444 00 Magnesium as Mg 0 00 0 00 0 00 0 00 0 00 0 00 0 00 Sodium as Na 0 00 0 00 0 00 0 00 0 00 0 00 0 00 Potassium as K 0 00 0 00 0 00 0 00 0 00 0 00 0 00 Iron as Fe 0 00 0 00 0 00 0 00 0 00 0 00 0 00 Axmonia as NH 0 00 0 00 0 00 0 00 0 00 0 00 0 00 Aluminum a Al 0 00 0 00 0 00 0 00 0 00 0 00 0 00 Boron as 0 00 0 00 0 00 0 00 0 00 0 00 0 00 ANIONS Chloride as Cl 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Sulfate as 504 159 6 239 4 319 2 399 0 478 8 558 5 528 23 Acidity 124 1 172 9 219 5 262 9 202 5 223 3 270 3 4 Alkalinity 111 0 166 4 221 8 277 1 232 2 387 3 442 3 P Alkalinity 1 0 2 0 6 5 11 9 19 2 26 5 29 5 Silica as 5102 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Phosphate as P04 0 0 0 0 0 0 0 0 0 0 0 0 0 0 H23 as H23 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Fluoride as F 0 00 0 00 0 00 0 00 0 00 0 00 0 00 Nitratce as 0 00 0 00 0 00 0 00 0 00 0 00 0 00 PARAMETERS pH 7 42 7 68 7 85 7 99 10 5 20 6 26 Temperature Deg F 122 00 122 00 122 00 122 00 122 00 122 00 122 00 Calculated T D S 413 15 612 92 610 40 1005 57 1195 77 1359 40 1577 59 DOSAGE 100 HEDP 0 04 0 11 0 2 0 53 0 90 2 08 4 59 42 The CHANGE RANGE and NEW TREATMENT selections on the menu bar when a graph is displayed work in a similar manner The Change Range option displays a smaller version of the graph with edit fields to change any relevant parameters OUTPUT PROPERTIES CHOOSE GRAPH NEW TREATMENT CHANGE RANGE Change Range El Calcite Saturatian Leve
16. A System ID specific to your computer Contact French Creek Software to obtain the installation will be C the Sust displayed Submit rogram say u opem Identific i b Press the the actual ID C ID tt tet displayed on opy mpm YOUR computer 203A FR8C 6DOE 6F7G CH2I CJ2K 4L another program Enter the Program Release Code in the field below Cap 1D Coie a Enter Program Release Code Here Calculated from System ID by French Creek TO OBTAIN A COMPUTER SPECIFIC PROGRAM RELEASE CODE 1 Copy the 26 character System Identification Code This System Identification will be displayed when you run the software until a Program Release Code is entered Each system will have a unique System Identification Code YOU MUST SUBMIT THE SYSTEM ID DISPLAYED ON YOUR COMPUTER NOT THE ID IN THIS MANUAL 2 Send this code to French Creek Software BY FAX TO 610 935 1008 BY E MAIL TO frenchcreek worldnet att net preferred method BY VOICE TO 610 935 8337 3 French Creek will respond with a System Release Code HELPFUL HINTS Press the COPY ID CODE button to copy the System Identification Number to the Windows clipboard Start an application such as a Word Processor or E Mail program Paste the System Identification Number into the application You might wish to Paste the number into the Subject field of an E Mail Or you might wish to paste it into the subject field of a FAX
17. EEE gt gt Low Temp 7o High Temp E 30 Evaluation Temp 1110 pH Control Method Alkalies Acids C Caustic soda NaOH C 98 H2504 Caustic potash C 35 HCI Soda ash Na2CO3 C 53 HN03 C Sodium bicarbonate NaHCO3 pH Target 7 oo C co2 C Lime Ca OH 2 NONE NONE pH Prediction Method C Default Curve C User GUWE Translate Source pH C Caplan Curve When you enter any of these modules a menu pops up requesting information on the minimum and maximum pH for the scenario calculations and on the minimum and maximum temperature for the calculations The typical pH is the pH which will be used for 2D plots which VARY TEMPERATURE The typical temp is the temperature which will be used for 2D plots which VARY pH When the 3D PROFILE is run both the pH and temperature ranges selected for the scenario are used for calculations Once a graph is displayed it can be printed from the options menu bar copied to the Windows clipboard and pasted into another application or saved as a PCX TIF or BMP file 37 COOLING TOWER WHAT IF All of the graphs can be generated using the Cooling Tower What If scenario modules The first step in generating any of the cooling tower graphs is to SELECT PARAMETERS for the scenario Parameters can be selected from the SELECT PARAMETERS module see form below The parameters you can vary include concentration ratio and increment whether or not to use acid
18. M MAKE SURE A FIXED WIDTH FONT SUCH AS COURIER IS SELECTED The table may lose all alignment when pasted into a word processing window with a variable width font e g Times New Roman selected as the current font If you encounter this don t despair 1 Go to the Word Processors SELECT ALL command The entire table should be highlighted 2 Go to the FONT selection menu for the word processor and select a fixed width font like Courier or Courier New 3 You may have to adjust the margins to the minimum or select a smaller sized font 45 46 WaterCycle R Models amp Predicts Corrosion Rate Load the product General Etch using the SELECT PRODUCT module to predict corrosion rates General Etch Corrosion Profile mmiyr or mpy mpy General Etch Corrosion Profile General Etch Corrosion Profile 45 03 40 04 85 04 n 30 04 m x ES a o N 25 0 o 3 20 0 15 04 10 04 5 0 e G D o 00 o o cr e e m m m Er T xs pH Temperature F De Hd WaterCycle Compares The Safe Operating Range For a Treated versus Untreated System Calcite Saturation Level 350 300 250 Saturation Level a so9 oAo 1e 3114044 SONVY ONILLvH3dO Cr gt amp or F T French Creek Software Treated vs Untreated Profile Examples The RED color code indicates potential trouble
19. THORITY Both parties warrant that all approvals necessary for the execution of this Agreement have been obtained and that the individuals signing the Order Form on behalf of their respective parties have full authority to do so 1 NOTICES Unless otherwise provided herein all notices or other communications under this Agreement must be in writing and signed by a duly authorized representative of the party giving such notice or such other persons as either party shall specify in a written notice to the other All such notices shall be deemed given and received when delivered by hand or placed in the mails addressed to the other party first class registered mail postage prepaid at the addresses indicated following the signatures of the parties on the Order Form or such other addresses as may be specified in writing 0 ENTIRE AGREEMENT The terms and conditions stated herein constitute the entire and exclusive agreement between the parties for the System and no other statements unless agreed to in writing shall be binding upon the parties No statement of any marketing representative shall be binding on French Creek unless set forth in writing and agreed to by French Creek This Agreement shall be effective only after its acceptance by French Creek at its offices in Pennsylvania k GOVERNING LAW This Agreement shall be governed and construed in accordance with the laws of the Commonwealth of Pennsylvania 76 TECHNICAL SUPPORT Via e
20. Version 7 Suite Compatible French Creek Software WaterC Cooling Water Modeling ycle Ka WaterCycle User Manual Copyright 2011 French Creek Software Inc All Rights Reserved The following are trademarks of French Creek Software Inc and may only be used with permission French Creek French Creek Software WaterCycle WaterCycle Rx hyd RO dose hyd RO sat DownHole SAT WatSIM and MineSAT The absence of aname or logo in this list does not constitute a waiver of any and all intellectual property rights that French Creek Software has established in any product feature or logos WaterCycle Rx Copyright 1999 French Creek Software Inc Kimberton PA 19442 All rights reserved Why Use WaterCycle Indices calculated by WaterCycle The WaterCycle Ry Series Getting Started Installation amp System Requirements Selecting Analytical Units Choosing Windows To Display Choosing Items To Print Carbonate Equilibrium Calculations Output Size On Screen What if Scenario Modeling Optimizing Treatments Selecting A Product Inputting A Product Formulation Developing Inhibitor Models Appendices and Bibliography Quick Reference Quick Start Disk Security System WHY USE WaterCycle WaterCycle allows a water treatment chemist to evaluate the scale potential for common scalants over the range of water chemistry temperature and pH anticipated in an operational
21. a input and some internal calculated values such as buffer capacity DIFFERENCE BETWEEN WaterCycle and the WaterCycle Rx Series The WaterCycle Rx series adds one or two pull down menus to the main WaterCycle menu The Salesman s Edition has one selection on the additional menu FORMULARY and one additional selection SELECT PRODUCT This module displays a list of the products on file and their description The Product Names and Descriptions listed are derived from the Product PRD files Printouts contain one additional line for the recommended dosage for the current product selected An additional graph selection is available for Product dosage profiles Although the Salesman s Edition of the program allows the use of the mathematical models and formulation data in the product file the original data cannot be accessed Someone with a product file cannot determine the active ingredients or their percentage in the formulated product The Product Manager s Edition adds a second additional selection to the FORMULARY menu INPUT PRODUCT The product s name description and formulation are entered in this menu to create a Product PRD file Only inhibitors for which you have Inhibitor INH files can be included in the formulations The Laboratory Edition adds a second additional pull down menu which is appropriately labeled LABORATORY Water chemistry data dosage temperature and the time period during which the water was stab
22. air tight systems For most systems carbonate calculations should be based upon the conservation of alkalinity Carbonate Equilibrium Calculations x Once Through CO Exchange with Atmosphere Conservative Properties Treat as an Open System Conserve Alkalinity Default C Conserve Carbon C Treat as a Closed System Default WARNING Most systems exchange CO2 with the atmosphere through open seals and other leakage sites Selection ofthe Closed System option can lead to extremely low predicted acid feed requirements for pH adjustment Cooling Towers CO Exchange with Atmosphere Conservative Properties Treat as an Open System Conserve Alkalinity Default Default C Treat as a Closed System C Conserve Carbon WARNING Operational Cooling Tower systems exchange CO with the atmosphere Selection ofthe Closed System option can lead to extremely low predicted acid feed requirements for pH adjustment Reset To Defaults Cancel You can select the appropriate method for carbonate calculations in the CO Calculations module which can be selected from the Preferences menu When in doubt conserve alkalinity 26 Selecting Windows To Display WaterCycle displays an enormous amount of information At times a total display is useful At other times two much information is confusing or a nuisance You can determine which informational outp
23. alculated values used to plot the 3D and 4D graphs can be exported as quotation mark comma delimited ASCII files These DAT files can be imported into most spreadsheet and graphics programs and used to recreate graphs or further manipulate the data 39 SETTING CONSTANT PHOSPHATE OR SILICA LEVELS The What if Scenario and Cycle modules will concentrate the phosphate in the make up water to the concentration ratio being evaluated unless you force it to maintain a constant recirculating concentration For example if there is 5 ppm of PO4 in a make up water the cycle module will use 25 ppm 5 ppm make up x 5 cycles for its calculations at a concentration ratio of 5 The Set Constant Values module allows you to override the default concentration of make up levels and substitute a constant value for calculations For example if you wish to evaluate a treatment program in the concentration ratio range of 3 to 5 at a constant phosphate level of 15 ppm use the Set Constant Values module to easily accomplish this modeling Select Constant Recirculating Water Concentration The Set Constant Values module can be used to set either constant phosphate levels constant silica levels or to maintain both at a constant level in the recirculating cooling water The Set Constant Value module can be accessed from the Make up Analysis input form Constant Values button or from the PREFERENCES pull down menu
24. as the ratio of the ion activity product of the reactants to the solubility product Saturation level can be defined as follows for common cooling system scalants based upon their respective solubility products For CaCO calcite and aragonite CO lt CaCO Saturation Level Ca CO3 Ksp where aCa is the activity coefficient for calcium aCO is the activity coefficient for carbonate Ca is the molar concentration of calcium CO is the molar carbonate concentration This relationship can be simplified if we incorporate the activity coefficients into the solubility product so that our examples can be expressed in a more readily viewed format The conditional solubility product incorporates the activity coefficients into the solubility product Ksp CaCO Ksp x 1 aCa x 1 aCO3 This notation Ksp will be used for the remainder of the examples For Calcium sulfate anhydrite Ca SO CaSO Saturation levelcasog Ca SOz Ksp casos For Silica SiO 2 H 0 gt H4SiO4 Saturation level SiO H4SiO H2O H20 Ksp Note that the activity of water is included in the calculation For tricalcium phosphate a higher order of reaction is encountered 3 Ca 2 PO4 gt Cas PO4 Saturation level Ca PO Ksp A higher order of reaction is also encountered for calcium fluoride Fluorite Ca 2 F CaF Saturation level Ca E Ksp and magnesium hydroxide Bruci
25. ationship with Customer In this regard Customer shall take all steps as are necessary or appropriate to fulfill this obligation In the event that Customer materially breaches its obligations under this section Customer understands and agrees that French Creek has the right to terminate this Agreement upon written notification to Customer Customer further agrees upon such termination to return to French Creek the original and all copies of the licensed System and related documentation Furthermore Customer acknowledges that French Creek shall be entitled to an injunction prohibiting the use and further disclosure of such licensed System and materials and further entitled to money damages resulting from such unauthorized disclosure The rights and remedies set forth herein are not exclusive and are in addition to any other rights and remedies provided by law and the exercise of one right shall not preclude the exercise of any other right stated herein The terms and conditions of this section shall survive any termination of this Agreement 73 8 MAINTENANCE Customer may elect to have French Creek perform maintenance services for the System by so indicating on the Order Form Maintenance services will commence upon Customer s execution of the Order Form and French Creek s receipt of the appropriate maintenance fee Maintenance services will be provided for an initial term of one year and will renew for additional one year terms unless eith
26. ccount for variation in dosage due to the effect of pH on the form in which the inhibitor exists see Hann and Bardsley When possible an experimental design should include five pH points The pH range studied should include the lowest and highest expected in the field THREE TO FIVE INDUCTION PERIODS PREFERRED Data should be run at a minimum of three different times to allow for the correlation of induction time versus inhibitor dosage In some test methods the times for each replicate will vary naturally In other methods dosages are evaluated at constant time extensions and the last dosage to provide 100 inhibition is selected as the minimum effective dosage Assure that the time spans covered by the data cover the full range over which you expect to use the model INCLUDE THE MINIMUM AND MAXIMUM FOR CRITICAL PARAMETERS Tests should ideally be run over the range of parameters under which the model will be used for inhibitor dosage recommendations For example the experimental design should include the minimum and maximum driving force where the model will be used If a calcium carbonate inhibitor is being evaluated the range of calcium and hardness levels anticipated should be bracketed as well as the range of calcite saturation levels RUN SUPPLEMENTAL TESTS WHERE APPROPRIATE Some inhibitors are known to lose activity in the presence of iron Tests run in the presence and absence of iron can help to expand the accuracy of models by allo
27. e Puckorius scaling index provides another tool for evaluating the calcium carbonate scale potential for a water and is included in the WaterCycle indices of calcium carbonate scale potential LARSON SKOLD INDEX The Larson Skold index describes the corrosivity of water towards mild steel The index is based upon evaluation of in situ corrosion of mild steel transport lines in systems transporting Great Lakes waters The index is the ratio of equivalents per million of sulfate SO4 and chloride Cl to the equivalents per million of alkalinity in the form bicarbonate plus carbonate HCO CO3 Larson Skold index _ epm SO _ HCO CO As outlined in their paper 6 the index correlated closely to observed corrosion rates and to the type of attack in the Great Lakes water study It should be noted that the waters studied in the development of the relationship were not alkalinity or buffering capacity deficient They were capable of forming an inhibitory calcium carbonate film if no interferences were present The results of the study demonstrate that chlorides and sulfates increase the aggressiveness of a cooling water with adequate buffering capacity and alkalinity to otherwise not be overly aggressive Perhaps the presence of chloride and sulfate interferes with the film formation which otherwise would be expected It must be noted that the Larson Skold relationship is based upon Great Lakes wat
28. e System to Customer French Creek agrees to indemnify defend and hold Customer harmless for breach of such warranty provided that Customer gives French Creek prompt notice of a claim alleging such breach and provided further that French Creek shall have full 72 authority to defend settle or compromise such claim If the use of the System provided hereunder is prohibited based on a claim of infringement of another party s rights then French Creek shall either a procure the right for Customer to use such licensed System b modify such portion of the System to become non infringing provided that such modification does not adversely affect Customer s intended use of the System as contemplated hereunder c replace the infringing portions of the System with equally suitable compatible and functionally equivalent non infringing programs and or other materials at no additional charge to Customer d if none of the above are commercially practicable then Customer shall terminate its use of the licensed System and accept from French Creek as compensation therefor all license fees paid hereunder less an amount equal to such license fees divided by 60 multiplied by the number of months of Customer s use of the System commencing with the date of System delivery This warranty and indemnity shall not apply if Customer is in material breach of this Agreement and such breach gave rise to French Creek s liability hereunder Similarl
29. ed are significantly lower than those based upon total analytical values The ion association model saturation levels have been in use by the major water treatment companies since the early 70 s The indices tend to give a more accurate indication of the driving force for scale formation They have not been in general use however due to the difficulty of calculating them The iterative approach required for the calculations mandates the use of a computer One of the purposes of WaterCycle is to make the ion association method for saturation levels available to all Water Treaters Saturation levels no matter how refined are still an equilibrium based index They provide a measure of the driving force for a scalant to form but do not incorporate the capacity of the water for continued scaling A water can have a high saturation level with no visible scale formation The driving force might be present but there is insufficient mass for gross precipitation Saturation levels should be viewed as another tool for developing an overall picture of a water s scale potential They can point out what scales won t form under the conditions evaluated but they can not predict that deposits of an economically significant quantity will form The next index covered incorporated the properties of quantity as well as driving force to round out the WaterCycle indicators of scale potential 10 MOMENTARY EXCESS PRECIPITATION TO EQUILIBRIUM This index i
30. elier saturation index pH pHs e pH is the measured water pH e pHs 15 the pH where the water will be saturated at equilibrium with respect to CaCO3 In the cooling water pH range of 6 5 to 9 5 the pH calculation simplifies to pHs pK pKs pCa pAlk e pK is the negative logio of the second dissociation e constant for carbonic acid e pK is the negative logo of the solubility product for calcite e pCa is the negative logo of calcium measured in the water e pAlk is the negative log of the total alkalinity measured for the water being evaluated WaterCycle uses the full iterative method for estimating the pH of saturation for calcite for calculating the Langelier saturation index The LSI is analogous to voltage for those who are electrically minded A voltage is the driving force for moving electrons across a resistance As voltage potential difference increases there is a higher driving force for current electron flow Voltage however indicates nothing of the current being moved The LSI and other saturation level based indices describe the driving force for scale formation and growth but say little of the amount of scale which will form or be dissolved in order to bring a water to equilibrium Although they are very useful a second factor must be considered in interpreting saturation level based indices Saturation level based indices indicate the potential for scale formation if a water is unperturbed for an i
31. elier saturation index provides an indicator of a water s degree of saturation with respect to calcium carbonate Saturation is referenced to the solubility product for a compound By definition the ion activity product of reactants e g Ca and CO3 is equal to the solubility product Ksp when the water is in equilibrium Ca aCa CO a CO Ksp A saturation level is defined as the ratio of the ion activity product to the solubility product Saturation level aCa Ca aCO CO Ksp If a water is under saturated with respect to calcium carbonate the saturation level will be less than 1 0 When a water is at equilibrium the saturation level will be 1 0 by definition although our estimation of the ion activity product or solubility product might be in error A water which is supersaturated with calcium carbonate will have a saturation level greater than 1 0 Saturation level is the driving force for crystal formation and crystal growth As the saturation level increases beyond 1 0 the driving force for calcium carbonate crystal formation or crystal growth increases It can be shown that the Langelier saturation index approximates the base 10 logarithm of calcite saturation level The Langelier saturation level approaches the concept of saturation using pH as a master variable 1 The Langelier saturation index can be interpreted as the pH change required to bring a water to equilibrium A water with a Langelier saturation index of 1 0 i
32. eptable and for the guidelines for the new All Organic programs 180 to 200 ppm operating in the pH range of 8 0 to 9 0 It is of particular importance to evaluate silica saturation level in systems with borderline solubility as cooling water temperature or pH decrease seasonally Magnesium silicate Mag silicate compounds do not necessarily form due to a stoichiometric reaction The author believes that magnesium silicate forms through the adsorption of silica onto precipitated magnesium hydroxide Brucite saturation level was added to WaterCycle calculated indices as a measure of the potential for magnesium silicate to form in a cooling system based upon this philosophy Ifa water is supersaturated with magnesium hydroxide Brucite and even low levels of reactive silica are present in the cooling water magnesium silicate formation is possible Magnesium silicate formation is probable when the water is supersaturated with Brucite and silica levels are 40 ppm as SiO2 or above A recent NACE paper reported the formation of stoichiometric magnesium silicate scales in cooling systems A stoichiometric form was added tot he scales evaluated by WaterCycle as a result of this paper Precipitation might be expected when the magnesium silicate saturation level exceeds 1 2 Calcium fluoride Treatment or operating parameter changes are recommended when the saturation level for Fluorite exceeds 1 0 Tricalcium phosphate Tricalcium phosphate sa
33. er party gives 60 days prior written notice of its intention to terminate such services Fees for renewal terms of maintenance services will be calculated as a percentage of the then current license fee for the System at time of renewal Under maintenance French Creek will provide Customer with periodic releases of the System that will include minor enhancements as well as modifications to keep the System operating in accordance with its accompanying documentation Prior releases of the System will be supported for three 3 months after a new release becomes available to Customer Support services under maintenance include telephone consultation and other reasonable services necessary to keep the System as supplied by French Creek performing in accordance with its documentation These services will be performed during French Creek s normal East Coast US business hours Ordinarily French Creek will be able to correct the problem over the telephone However if requested by French Creek Customer will document the circumstances giving rise to such problem and provide such explanation to French Creek in writing If French Creek is unable to correct the problem within 48 business hours of receipt of such written explanation and such problem prevents normal operation of the System consistent with its documentation French Creek will provide Customer with another copy of the System to help resolve the problem If it is determined that the problem was cau
34. erived indices only account for the driving force for calcium carbonate scale formation They do not account for two other critical parameters the buffering capacity of the water and the maximum quantity of precipitate that can form in bringing a water to equilibrium A water high in calcium but low in alkalinity and buffering capacity can have a high calcite saturation level The high calcium level increases the ion activity product A plot of ion activity product versus precipitate for the water would show a rapid decrease in pH as calcium precipitated due to the low buffering capacity Even minuscule decreases in carbonate concentration in the water would drastically decrease the ion activity product of the water due to the small quantity present prior to the initiation of precipitation The water might have a high tendency to form scale due to the driving force but scale formed might be of such a small quantity as to be unobservable The water has the driving force but no capacity and no ability to maintain pH as precipitate forms The Puckorius scaling index is calculated in a manner similar to the Ryznar stability index Puckorius uses an equilibrium pH rather than the actual system pH to account for the buffering effects Puckorius scaling index 2 pHs WaterCycle calculates the pH for this index using the rigorous iterative method Puckorius formula for pH 5 is used PHeq 1 465 x logyo M Alkalinity 4 54 Th
35. ers Extrapolation to other waters such as those of low alkalinity or extreme alkalinity goes beyond the range of the original data Such extrapolations should be closely scrutinized or weighted lightly Most water treaters will agree however that the aggressiveness of a water increases with increasing chloride and or sulfate levels and that corrosivity also increases with decreasing alkalinity The index has proven a useful tool in predicting the aggressiveness of once through cooling waters It is included in WaterCycle due to the preponderance of waters of composition similar to the Great Lakes waters and due to its potential usefulness as in indicator of aggressiveness in reviewing the applicability of corrosion inhibition treatment programs which rely heavily on the natural alkalinity and film forming capabilities of a cooling water The index might be interpreted by the following guidelines Larson Skold Indication lt lt 0 2 chlorides and sulfate probably will not interfere with natural film formation gt gt 0 2 but lt lt 0 6 X chlorides and sulfates may interfere with natural film formation Higher than desired corrosion rates might be anticipated gt gt 0 6 the tendency towards high corrosion rates of a local type should be expected as the index increases SATURATION LEVEL Saturation level has been previously discussed as the basis for many of the common indices used by water treaters The saturation level is defined
36. es and is referred to as Saturation Level Degree of supersaturation and x Saturation This ratio will be referred to as Saturation Level or Degree of supersaturation throughout the manual The following general guidelines can be applied to interpreting the degree of supersaturation 1 If the saturation level is less than 1 0 a water is under saturated with respect to the scalant under study The water will tend to dissolve rather than form scale of the type for which the index was calculated As the saturation level decreases and approaches 0 0 the probability of forming this scale in a finite period of time also approaches 0 2 A water in contact with a solid form of the scale will tend to dissolve or precipitate the compound until an IAP Ksp ratio of 1 0 is achieved This will occur if the water is left undisturbed for an infinite period of time under the same conditions A water with a saturation level of 1 0 is at equilibrium with the solid phase It will not tend to dissolve or precipitate the scale 3 As the saturation level IAP Ksp increases above 1 0 the tendency to precipitate the compound increases Most waters can carry a moderate level of supersaturation before precipitation occurs in a finite period of time such as the seconds to minutes a water is present in a once through cooling system or the hours to days a water is present in a cooling tower system Most cooling systems can carry a small degree of supersaturation The
37. for pH control and the pH Alkalinity relationship to use for predicting pH as the water cycles Run the SELECT PARAMETERS module prior to CYCLE or any of the OPERATING RANGE PROFILES Select Cycled Parameters E qe Concentration Ratio gt Flange For Cyeted ater F hd ae p Acids gt Caustic soda NaOH J ge H250 p C HCL Soda ash Na2C03 BEN S HNOS 221 Sodium bicarbonate MsHCOS E ym cu ur m Le Hee E d c pH Control Method pH Prediction Method n Wal Table And 2D Graphs SII a 4D Maximum 25 And a Tapia Cancel 38 CYCLING COOLING WATER AND CALCULATING INDICES VERSUS CONCENTRATION RATIO The Cycle module concentrates the cooling tower make up water Water is cycled according to the Start Maximum and Increment entered in the WaterCycle PARAMETERS menu under the Concentration Ratio heading The water is cycled at the Typical Temperature entered If pH control is selected the appropriate acid is used to maintain a maximum of the Control pH selected Tables summarizing the recirculating water chemistry and calculated indices are displayed upon completion of the CYCLE module The indices can be graphed in 2D format versus concentration ratio using the GRAPH module The tables can be printed from the Options Menu Bar when they are displayed on the screen or by selecting the Cycled Water m
38. gh a significantly higher hydroxylapatite saturation level can be carried in the presence of a copolymer terpolymer or other calcium phosphate scale control agents Iron carbonate Siderite the mineral name for iron carbonate is usually found in conjunction with calcium carbonate scale in cooling system Iron carbonate scale can be expected when the saturation level exceeds 1 2 Amorphous iron hydroxide Iron hydroxide precipitation can be expected in cooling water when the saturation level exceeds 1 0 a very common situation when iron is present Iron may precipitate in the bulk water as iron hydroxide but not form scale in high flow rate systems Remedial action such as a dispersant should be taken in systems with high iron hydroxide saturation levels Note that iron hydroxide momentary excess values reported will almost always be negligible This ids due to the high order of the reaction Rely upon the saturation level for deposition prediction and ignore the momentary excess in most cases Tron phosphate Strengite the iron phosphate mineral modeled by WaterCycle should be considered a problem when the saturation level exceeds 1 0 Momentary excess for this scale former will be negligible in most cases due to the low level of free phosphate typically available Rely upon the saturation level for prediction of iron phosphate scale CaCO Scale amp Corrosion Potential As Inferred From Simple Indices The Langelier Saturation Inde
39. h Customer may utilize WaterCycle Rx is not intended as a substitute for the exercise of judgment by Customer s employees or consultants These terms and conditions state the legally binding understandings between French Creek and Customer relating to the licensing of the System and the performance of services indicated in the French Creek Software Order Form Order Form The terms of this Agreement are incorporated by reference into the Order Form 1 WaterCycle Rx Customer desires to license WaterCycle Rx as indicated by Customer on the Order Form and more fully described in its accompanying documentation The System documentation indicates the equipment configurations which may be used to operate WaterCycle Rx and is hereby incorporated by reference Customer should specify on the Order Form the number of copies of the System to be licensed under this Agreement 2 DELIVERY AND SUPPORT French Creek will ship the number of copies of WaterCycle Rx as indicated on the Order Form as well as System documentation upon French Creek s receipt and acceptance of an executed Order Form and accompanying fees Delivery will be made at a mutually agreeable time but no later than thirty 30 days after French Creek has accepted the Order Form Payment of applicable fees is due upon execution of the Order Form WaterCycle Rx is capable of being installed by Customer by following the installation instructions in the documentation As part of the lice
40. he right to terminate any service provided hereunder as stated herein or in the Order Form 12 GENERAL a AMENDMENT No amendment or supplement to this Agreement shall be binding unless consented to in writing and signed by both parties provided that such consent shall not be unreasonably withheld The party requesting any consent under this Agreement shall reimburse the other party for any expenses including attorneys fees which result from the request for consent b ASSIGNMENT Neither party may assign sub license sub lease lend rent or otherwise transfer this Agreement or the rights granted hereunder to any person whether by operation of law or otherwise without the other party s prior written consent which consent shall not be unreasonably denied PROVIDED HOWEVER that no consent shall be required for any assignment or transfer Pursuant to any merger consolidation or reorganization to which either Customer or French Creek is a party This Agreement shall bind and inure to the benefit of any such successor or assign The license granted hereunder shall not be assigned or assignable in any proceeding involving the liquidation of Customer c RELATIONSHIP OF THE PARTIES It is clearly understood between the parties that at all times during this Agreement that the relationship between French Creek and Customer is solely as independent contractors and in no other capacity The parties agree that there are no intended or incidental
41. ignifies that a problem will occur with a minimum of change Make sure of your measurements A slight error in pH could mean that you are really operating in a RED zone The system is borderline and should be watched GREEN No problems are likely Significant changes e g a 0 1 pH increase a 10 C increase could result in a problem BLUE Blue signifies a safe operating range where deposition from the scale evaluated would not be expected Blue is also used to signify a successful treatment in TREATED SYSTEM PROFILES Dosage Profiles RED Red signifies a definite problem prediction The treatment will not work regardless of dosage level The system is out of range e g too high a saturation level for the treatment selected MAGENTA Magenta purple signifies that a problem is approaching or highly likely In the case of calcium carbonate inhibitors MAGENTA signifies that the system is within ten 10 percent of the limit for the inhibitor e g 135 calcite saturation level to 149 calcite saturation level for an inhibitor that fails at 150 or above In the case of blended orthophosphate copolymer products MAGENTA signifies that insufficient polymer is present for calcium phosphate scale control when the product is dosed at the level required for adequate corrosion protection The corrective action is to increase the ratio of copolymer to phosphate BLUE Blue signifies a safe operating range where the treatment will prevent dep
42. ing the phosphate treated water Select a zinc inhibitor package for product 1 and a scale control zinc stabilization package for product 2 You could also select a scale control product for product 1 and a silica dispersant inhibitor for product 2 Version 6 provides the additional sequential product evaluation capability especially to optimize phosphate treatments It is recommended that single products be selected as product 1 55 INPUTTING A PRODUCT FORMULATION The Input Product module in the FORMULARY pull down menu is used to create a product PRD file The Input Product module is available only in the WaterCycle Rx Product Manager and Laboratory Editions inhibitor Formulation ninpot Form x m 000 DD 0 000 msc S oom Combos Lone eee E f 0 000 sa un 0 000 ie peer cm 56 Use the Input Product module to create a new product file or modify an existing product file s Product Name Description or Formulation All entries are made in the form reproduced on the next page The Product Name and Description information entered are stored in the product file and used as the Product Name and Description list in the Select Product module pop up menu Inhibitors MUST be selected from the pop up menu list of available inhibitors on file Move the cursor to the Inhibitor Field Click on the button next to the ingredient field to pop up the list of available
43. ing the printout in the computer s memory prior to transmitting to the printer Choose Direct Print initially Change your selection to Indirect Print if problems are encountered printing graphs Choose Print Mode 31 32 What if Scenario Modeling Introduction Once Through What if Cooling Tower What if Setting Constant Phosphate or Silica Levels Predicting pH Report Options Copy to the Clipboard Print Choosing lonsiScales to Print and CopylPaste Change Range Change Treatment Tables Graphs Suggested Work Flow Diagrams Once Through Open Recirculating Cooling Tower 33 34 WHAT IF SCENARIO MODELING What if scenario modeling provides one of the greatest benefits from using WaterCycle The WHAT IF SCENARIO modules allow you to visualize what will happen to the scale potential and corrosivity of a cooling water as operating parameters and water chemistry change The What If scenarios allow you to evaluate the current cooling water over the entire range of operating parameters The What If s also provide a predictor for use in evaluating new cooling systems and as an aid in establishing control ranges and operating parameters For once through cooling systems the What If scenarios allow you to evaluate the scale potential of a cooling water over the temperature range expected and the pH range encountered Input parameters for selecting the What If scenario ranges include minimum and maximum
44. inhibitors Select the inhibitor of interest The inhibitor file will be loaded for the ingredient selected ENTER THE IN THE FORMULATION BASED UPON 100 ACTIVE INGREDIENTS e g if you are using a material which is 50 active AMP and you wish to have the product be 10 active you would enter 20 on a manufacturing batch sheet for the material on an as is basis Enter 10 on the WaterCycle Rx formulation sheet for the material on an active basis WaterCycle will 1 total the active ingredients and balance the formula with water Pressing the OK button saves the formulation and inhibitor information in the product PRD file named in the File Name field Copies of this file can be distributed to users of the WaterCycle Rx Salesman Edition program NOTE Inhibitors should be re loaded into a formulation sheet when an inhibitor file is updated Product files load a copy of the inhibitor file when they are created They DO NOT automatically re load a new file when the inhibitor data is updated The module accepts input data for a product file loads the mathematical correlations for the individual inhibitors in the formulation and outputs the new or updated product file An inhibitor file INH must be in the WATER INHIB sub directory for each inhibitor which is an active ingredient Inhibitor files are created in the Input Lab Data module of the LABORATORY pull down menu in the WaterCycle Rx Laboratory Editions They can be created
45. l 3 221 18 gt u a g a e a 1 m w e A Canceniration Rallo low cycles C R high cycles Cancel Concentration Ratio 43 The NEW TREATMENT option displays the CHOOSE PRODUCT menu over the current graph or table OUTPUT PROPERTIES CHOOSE GRAPH NEW TREATMENT CHANGE RANGE Calcite Saturation Level SELECT PRODUCT L 100 ACUMER 2000 Ca PO4 Inhib 100 ACUMER 3100 Ca POA Inhib 1100 ACUMER 5000 5102 Inhibitor 1100 AMP CaCO3 INHIBITOR 100 HEDP CaCO3 INHIBITOR 1100 OPTIDOSE 2000 Ca POA Inhib 100 OPTIDOSE 3100 Ca POA Inhib 100 orthophosphate corrosion inhib 100 PAA CaCO3 INHIBITOR 1100 PBTC STRESSED CaCO3 1010 Carbon Steel General Etch AQUATREAT AR 540 Ca POA Inhib BELCLENE 161 CaS04 Inhibitor Cancel These new features are common throughout the French Creek Software product line Other menu bar selections such as PROPERTIES and OUTPUT allow you to further customize a graph or table Use PROPERTIES to switch a graph from treated to untreated color coding or from bar graph format to contour PROPERTIES also can switch between grey scale and color display and printing PROPERTIES also allows the reversal of axis when appropriate The OUTPUT selections include Copy to the clipboard which will copy a table or graph to the clipboard for pasting into another application 44 NOTE WHEN COPYING A TABLE TO A WORD PROCESSING PROGRA
46. le are entered into the RAW DATA INPUT module Once data is entered multiple regression is used to develop a model and determine the goodness of fit between your data and the model This module generates Inhibitor files for use by the Product Manager version of the program or the related modules in the Laboratory version Note the Laboratory version can perform any function done by the Salesman s or Product Manager Versions 18 WaterCycle Rx Files The WaterCycle Rx series uses three 3 file types in addition to those generated by the original WaterCycle program The original files included the WAT work files and the PCX graphic output files The Rx series adds the PRD product information file the INH inhibitor correlation file and the COR laboratory data for correlation file Original WaterCycle Files WAT workspace files store water analysis entered into WaterCycle units information What if parameters and any indices which were calculated prior to being stored in file format WAT files are WaterCycle work files which allow you to stop work save what you have completed and return at another time A WAT file returns the WaterCycle program analysis and values to the same condition they were when the file was saved CHM chemistry files store water analysis entered into WaterCycle Only water chemistry parameters are overwritten when a CHM chemistry file is loaded This allows you to load the same makeup o
47. low buffer capacity Puckorius 5 also warned against using saturation level derived indices as the basis for foretelling corrosion problems in cooling systems The Langelier saturation index is elegantly derived in the original published form 2 It is also thoroughly explained by Lowenthal and Marais 4 RYZNAR STABILITY INDEX The Ryznar stability index attempts to correlate an empirical data base of scale thickness observed in municipal water systems to the water chemistry Like the Langelier saturation index the Ryznar stability index has its basis in the concept of saturation level Ryznar attempted to quantify the relationship between calcium carbonate saturation state and scale formation The Ryznar index takes the form Ryznar stability index 2 pHs pH The empirical correlation of the Ryznar stability index can be summarized as follows RSI lt lt 6 scale tendency increases as the index decreases RSI gt gt 7 calcium carbonate formation will probably not lead to a protective corrosion inhibitor film RSI gt gt 8 mild steel corrosion becomes an increasing problem WaterCycle uses the pH calculated by the rigorous iterative method for RSI estimation PUCKORIUS SCALING INDEX The Puckorius or Practical scaling index attempts to further quantify the relationship between saturation state and scale formation by incorporating an estimate of buffering capacity of the water into the index The previously discussed saturation d
48. m as a system simulator To save time WaterCycle can calculate and save the indices you currently calculate by hand and store the water analyses and calculated indices In many cases WaterCycle allows you to prepare presentation quality graphical profiles in about the same time it would take to manually calculate the Langelier and Ryznar indices WaterCycle provides a complete profile for the manpower cost of calculating a few indices using a nomograph or cooling water slip stick Additionally the Rx series develops models of inhibitor performance and optimizes treatment program applications WHAT INDICATORS DOES WaterCycle CALCULATE WaterCycle calculates indicators of scale potential for calcium carbonate tricalctum phosphate hydroxylapatite silica calcium sulfate calcium fluoride magnesium hydroxide magnesium silicate iron hydroxide iron carbonate and iron phosphate It also calculates a corrosivity index based upon the work of Drs Larson and Skold on the corrosivity of Great Lakes waters towards mild steel e Indices calculated over the range of operating conditions specified include e the most common Langelier and Ryznar e an evolving and currently being promoted index Puckorius e those that have been used by the major water treatment companies but have generally been unavailable to most water treaters Saturation levels based upon an ion association model e and some that the program author has found useful and
49. mail frenchcreek worldnet att net At Our Web Site http www frenchcreeksoftware com By Telephone Voice 610 935 8337 FAX 610 935 1008 SOFTWARE UPDATES At Our Web Site Registered users with active Annual Maintenance Agreements can download updates from our web site A USER ID and PASSWORD is required To register for a USER ID and PASSWORD Visit our web site and REGISTER FOR UPDATES To download updates visit the LICENSED USER DOWNLOAD AREA http www frenchcreeksoftware com FAST TRACK INSTALLATION Insert the diskette in floopy drive A or B Execute the program SETUP EXE from FILE MANAGER or Use the Windows RUN command to launch SETUP EXE Be sure to install to the WATER directory e g C WATER or DAWATER Z WATER To Execute WaterCycle R Click on the Cooling Tower icon or use the run command for WATER WATWIN EXE Click on the START Button in Win95 98 2000 Me XP or NT and select the WaterCycle icon in the French Creek program group The Security System The software is protected against unauthorized access To activiate the software you must obtain a Program Release Code from French Creek Software The following dialog box will appear when the software is run prior to activating with a Program Release Code System Identification Code submit the actual System ID displayed on your computer to French Creek to receive your computer installation specific Program Release Code Example
50. ment 10 LIMITATION OF LIABILITY French Creek s liability during the 30 day period following delivery of the System shall be limited to attempting to repair any System error condition or to accept return of the System and refund to Customer all related license and initial maintenance fees exclusive of travel living and out of pocket expenses paid to French Creek on account of this Agreement Thereafter French Creek s liability to Customer shall not exceed the amount of license fees paid to French Creek on account of the System French Creek shall have no liability to Customer for damages resulting from causes beyond French Creek s reasonable control IN NO EVENT WILL FRENCH CREEK BE LIABLE FOR ANY SPECIAL INDIRECT OR CONSEQUENTIAL DAMAGES INCLUDING LOSS OF PROFITS OR GOODWILL ARISING FROM OR IN CONNECTION WITH THE SYSTEM OR SERVICES PROVIDED UNDER THIS AGREEMENT EVEN IF FRENCH CREEK IS ADVISED OF THE POSSIBILITY OF SUCH DAMAGES THIS SECTION STATES CUSTOMER S EXCLUSIVE REMEDIES UNDER THIS AGREEMENT THIS SECTION SHALL SURVIVE ANY TERMINATION OF THIS AGREEMENT 11 TERM AND TERMINATION The license granted in this Agreement is for a term of twenty 20 years or until sooner terminated as stated herein Upon termination Customer shall return to French Creek the original and all copies of the licensed System and related documentation or certify in writing to French Creek the destruction of such materials French Creek reserves t
51. national Water Conference 1991 15 Gill J S Anderson C D and Varsanik R G Mechanism of Scale Inhibition by Phosphonates Proceedings of the 44th International Water Conference 1983 69 16 Boffardi B P Schweitzer G W Advances in the Chemistry of Alkaline Cooling Water Treatment Corrosion 85 Paper 132 17 Ashcroft R H Scale Inhibition Under Harsh Conditions By 2 Phosphonobutane 1 2 4 Tricarboxylic Acid Corrosion 85 Paper 123 18 Hann W M Natoli J Acrylic Acid Polymers and Copolymers as Deposit Control Agents in Alkaline Cooling Water Systems Corrosion 84 Paper 315 19 Amjad Z Masler W F III The Inhibition of Calcium Sulfate Dihydrate Crystal Growth by Polyacrylates and the Influence of Molecular Weight Corrosion 85 Paper 357 70 WaterCycle Rx LICENSE AGREEMENT FRENCH CREEK SOFTWARE INC FRENCH CREEK Kimberton amp Hares Hill Road Box 684 Kimberton PA 19442 French Creek has developed the automated capability to predict certain chemical properties of water samples French Creek refers to this computer software as WaterCycle Rx sometimes referred to as WaterCycle Rx or System in this Agreement WaterCycle Rx is a predictive tool which will enable Customer to obtain a more complete understanding of the chemistry of the water being analyzed WaterCycle Rx should be used as a supplement to Customer s historical experience and other testing procedures whic
52. nfinite period of time Most cooling water systems have a substantially shorter holding time index A final point on the Langelier index deals with the concept of corrosivity The LSI was not intended as an indicator of corrosivity towards mild steel or other metals of construction The LSI describes only the corrosivity of a water towards an existing calcium carbonate scale or other calcium carbonate bearing structure The LSI does describe the tendency of a water to dissolve corrode calcite scale It has also been used to control the corrosion of asbestos concrete board ACB fill which uses calcium carbonate as part of the binder Water is adjusted to be non corrosive to ACB fill by increasing the pH to a saturated non corrosive LSI But the interpretation of corrosivity towards metals is not explicit in the LSI It has been postulated that a supersaturated water will form an eggshell like film of calcium carbonate scale which will act as an inhibitor film for corrosion of mild steel This can occur in highly buffered waters The LSI or other saturation based indices do not guarantee this inhibitory behavior Calcium carbonate film formation is typically observed in highly buffered waters Researchers Stumm 3 Lowenthal and Marais 4 have shown that waters supersaturated with calcium carbonate often develop tubercular deposit which do not inhibit corrosion on mild steel This behavior is typically associated with waters of
53. nn Arbor Science 1982 5 Puckorius Paul Getting A Better Reading on Scaling Tendency of Cooling Water Power September 1983 6 Larson T E and Skold R V Corrosion 14 1958 7 Truesdell A H and B F Jones WATEQ A Computer Program for Calculating Chemical Equilibria in Natural Waters N T I S Publication PB220460 1973 8 Schell Charles J The Use of Computer Modeling in Calguard to Mathematically Simulate Cooling Water Systems and Retrieve Data Proceedings of the 41 rst International Water Conference 1980 9 Chow Winston Aronson John T Michletti Wayne C Calculations of Cooling Water Systems Computer Modeling of Recirculating Cooling Water Chemistry Proceedings of the Alrst International Water Conference 1980 10 Johnson Donald A Fulks Kenneth E Computerized Water Modeling in the Design and Operation of Industrial Cooling Systems Proceedings of the 41rst International Water Conference 1980 11 Musil R R and H J Nielsen Computer Modeling of Cooling Water Chemistry Proceedings of the 45th International Water Conference 1984 12 Ferguson R J A Kinetic Model for Calcium Carbonate Deposition Materials Performance November 1984 13 Caplan Gary Cooling Water Computer Calculations Do They Compare Corrosion 90 Paper 100 14 Ferguson R J Computerized Ion Association Model Profiles Complete Range of Cooling System Parameters Proceedings of the 52nd Inter
54. nse fee French Creek provides 30 days of technical support Technical support refers to assisting Customer to learn how to operate WaterCycle Rx but does not include technical assistance in the interpretation of the various indices calculated by WaterCycle Rx If additional assistance is required French Creek will use its best efforts to assist Customer and will charge Customer for such services at its then current consulting charges 3 PAYMENT The fees and payment terms for the System and services are set forth in the Order Form Customer shall be responsible for the payment of any and all taxes or amounts paid in lieu thereof however designated levied or based on the System license granted hereunder or upon the services to be rendered or otherwise on account of this Agreement exclusive only of taxes based on French Creek s net income French Creek reserves the right to terminate the System license for failure to pay related license fees or taxes and or to terminate any service for failure to pay related service fees or taxes as stated in the Order Form 4 CONDITIONS TO SYSTEM LICENSE French Creek hereby grants Customer a license to operate the System subject to the terms and conditions of this Agreement The WaterCycle Rx license is a non exclusive non transferable right to use the System Failure to abide by any of the conditions stated in this Agreement may result in termination of the license granted in this Agreement The WaterC
55. odule in the REPORTS menu The Options Menu Bar also contains options to Copy the rpeort to the Windows clipboard for pasting into another application such as a word processor 3D OPERATING RANGE PROFILES This module uses the Operating Range Specification to model the operating range at the Typical Concentration Ratio over the Low to High Temperature range and the Low to High pH range IF an acid pH control option was selected pH control is used Graphs can be displayed as 3D bar graphs or as 3D contour plots The Options Menu Bar has selections to toggle the graph type from 3D Bar to 3D contour when a bar graph is displayed and to toggle the graph type between 3D Contour and 3D Bar plots 4D OPERATING RANGE PROFILES The 4D profiles calculate and plot the indices over the Low to High pH and Temperature operating range entered in the PARAMETERS menu The indices are calculated at both the Low and the High Concentration Ratio entered 4D bar graphs are Minimum Maximum bar plots 4D contour plots stack the Low and High concentration ratio profiles FEATURES COMMON TO ONCE THROUGH AND COOLING TOWER GRAPHS The CHOOSE GRAPHS module can be used to select the graphs desired It presents an identical menu of graphs as the CHOOSE GRAPHS options on the menu bar at the top of a displayed graph Once a graph is displayed on the screen it can be saved as a PCX BMP or TIF file for use in other programs such as word processing programs or printed C
56. ooling system and its water treater WaterCycle calculates theses indicators over the operating parameter ranges you specify and presents them in graphical as well as tabular form The indicators are applicable to both once through cooling waters and open recirculating cooling tower systems WHEN TEMPERED BY YOUR EXPERIENCE AND KNOWLEDGE OF WATER TREATMENT The program can be applied to long as well as short residence time systems WaterCycle can assist the cooling tower operator or water treater in establishing control limits based on concentration ratio cycles of concentration pH and temperature profiles The program can help estimate sulfuric or Hydrochloric acid requirements to maintain a prescribed pH control point In summary you should use WaterCycle 1 To develop an overall profile of scale potential for common cooling system scalants over the entire range of critical operating parameters anticipated To evaluate the scale potential of an open recirculating cooling system versus concentration ratio as an aid in establishing control limits To evaluate the benefits of pH control with respect to scale potential and to estimate acid requirements To quickly review these indicators as water quality changes or environmental constraints force operation with reduced water quality and increased scale potential To learn more about the interaction of water chemistry and operating conditions pH temperature by using the progra
57. or allow use of the System in any time sharing or service bureau arrangement or with any interactive cable system or local area network Customer may only use the System for its own internal business or in servicing the business requirements of its clients for whom Customer performs services c Customer shall not release or allow the release of the System or its related documentation in any form to any third party except to Customer s employees who are directly concerned with the licensed use of the System except as otherwise specifically stated herein d Customer shall not copy the System except for purposes of normal backup and testing without the prior written consent of French Creek In the event that Customer copies the System or its accompanying documentation as stated herein Customer agrees to also copy French Creek s copyright notices and or other proprietary notices in the same manner location and method of presentation as existed in the materials supplied by French Creek to Customer e Other than as stated in this Agreement Customer understands and agrees that it has no right title or interest in the System and agrees that it shall not attempt at any time to transfer its rights to use the System without the prior written consent of French Creek Customer agrees that it will not use System except as stated herein Customer further agrees that it will not modify decompile or disassemble the System nor shall Customer incorporate
58. orted into newer version of WaterCycle Rx Older models are as follows 1 Model 0 Dosage f DF 1 time The first model develops a correlation of dosage as a function of driving force temperature and time The driving force selected for this or other models should be appropriate for the scale forming species under study For example calcite saturation level is a common driving force used to model calcium carbonate scale inhibitors Tricalcium phosphate saturation level is a recommended driving force for use in modeling the effectiveness of calcium phosphate control agents Gypsum saturation level is recommended for modeling calcium sulfate control at low lt 130 F temperature while anhydrite saturation level might be more appropriate at higher temperatures This model subtracts 1 0 from the saturation levels This accounts for the driving force for scale formation not being present until the test water becomes supersaturated at a saturation level above 1 0 2 Model 1 Dosage f DF time The second model differs from the first in that the correlation is developed to the raw driving force rather than to the driving force 1 3 Model 2 Dosage f DF 1 time pH The third model is identical to model 0 with one exception pH is included as a variable to account for the impact of pH upon the form in which an inhibitor exists This is typically the model of choice for developing a correlation for a scale inhibitor 4 Model 3 Corro
59. osition of the scale evaluated 15 16 Saturation Level iim WaterCycle s Fuzzy Chemistry Profiles Predict Problems Over A Broad Range of Operating Conditions Calcite Saturation Level 20 0 15 0 10 0 5 0 0 0 Color coding identifies the severity of the problem Blue signifies a safe range Green indicates a mild problem potential if conditions change slightly Yellow warns you to check measurements trouble is near Magenta indicates a problem is likely Take corrective action Red warns of a problem Treatment or other remedial action is required SOJOAD Of 1e dilHOud ADNYY ONILLvH3dO WaterCycle Rx Series Most of us use our own system for varying inhibitor treatment levels with water chemistry Over the years we ve developed our own rules of thumb For example e Most of use apply higher levels of inhibitors as temperature increases e Most of us increase dosage as the driving force for scale formation increases Higher levels of CaCO3 inhibitors are applied as the Langelier Saturation index or calcite saturation level increase e Many of us will feed higher inhibitor levels to a 72 hour holding time index system than to a 3 hour residence time system We will definitely feed higher levels to a long holding time cooling tower than to a once through cooling system e And finally most of us will feed a slightly higher dosage in high pH systems All other things being equal dosages for
60. perating system Performance increases with memory and processor speed Suggested minimums are as follows Windows 3 1 Windows 95 Windows NT Processor 80386 Minimum 80486 DX2 66 Pentium 75 RAM Memory 8 Megabytes 8 Megabytes 12 Megabytes 12 Preferred 16 Preferred Hard Drive 4 Megabytes 4 Megabytes 4 Megabytes Space VGA 640 x 480 VGA 640 x 480 VGA 640 x 480 Video SVGA 800 x 16 SVGA 800 x 16 SVGA 800 x 16 preferred preferred preferred Notes Math Coprocessor Math Coprocessor Math Coprocessor required required required Please note that each workspace file will consume up to 50K of hard drive space Each graph stored as a PCX file will use around 50K Each graph stored as a BMP file can take up to 600K of hard drive space If you choose to install the program on a 386 or 486 system insure that a math coprocessor 80386 80387 or 486SX 487SX or 486DX Pentium processors and equivalents include a math coprocessor 23 INSTALLATION BEFORE YOU DO ANYTHING ELSE WHY NOT MAKE A BACKUP COPY OF THE PROGRAM DISK S PUT THE ORIGINAL DISKETTE S IN A SAFE PLACE AND USE THE BACKUP AS YOUR WORKING INSTALLATION DISK WRITE PROTECT THE BACKUP DISKETTE S ONCE THE COPY IS MADE The program is installed like most Windows software by running the SETUP EXE file on the installation diskette 1 Insert the program diskette in the floppy drive 2 Use the Windows RUN command to execute A SETUP EXE lt press enter gt You can also exec
61. r source water analysis into a variety of systems without re entering the water chemistry manually SPC system specification files store system specifications entered into either the once through or cooling water specifications input form System specification files only overwrite parameters such as cooling water flow rate residence time holding capacity etc when loaded This allows a chemistry file and a specification file to be retreived to complete a work space PCX files are a standard graphic format used to store pictures on the screen for transfer to other programs WaterCycle creates a type 5 PCX file with all color palette information stored as well as the graphic information BMP files are a standard windows graphic format BMP bitmap files store the same einformation as PCX files but tend to be significantly larger TIF files are a third graphic format used to store pictures on the screen for transfer to other programs WaterCycle Rx Salesman Edition Files The Salesman Edition creates the same files WAT SPC CHM and graphic files that are created by the original WaterCycle program The Salesman Edition WAT file includes any dosage recommendations calculated prior to the file being saved as well as information on the current product The Salesman Edition uses but cannot create modify or display product information files PRD PRD files contain product formulation information such as active ingredients
62. realistic Momentary excess and the Larson Skold index A detailed review of these indices is included in a later section of this manual and in references in the bibliography WHAT WaterCycle WON T DO WaterCycle will not recommend a treatment program It will not turn the computer screen red and scream Your scale inhibitor can not handle this high a calcite saturation level at this temperature and this residence time You will have to provide the interpretation based upon your and your water treatment company s knowledge of inhibitor effective limits WaterCycle Rx programs will provide guidelines for treatment levels and where inhibitor limitations are known warn you of projected inhibitor failure through color coding Dosages turn RED when out of range The Langelier Saturation Index The Langelier Saturation index LSI is a purely equilibrium model derived from the theoretical concept of saturation A water is said to be saturated with calcium carbonate when it will neither dissolve or precipitate calcium carbonate scale This equilibrium condition is based upon an undisturbed water at constant temperature which is allowed to remain undisturbed for an infinite period of time A water is said to be under saturated if it will dissolve an existing calcium carbonate substrate if left at rest for the same infinity A supersaturated water will precipitate calcium and carbonate from a water if allowed to rest The Lang
63. s adapted from a little used calculation of Momentary Excess This index describes the quantity of scalant which would have to precipitate instantaneously to bring a water to equilibrium In the case of calcium carbonate Ca CO3 Ksp at equilibrium If a water is supersaturated Ca CO3 gt gt Ksp Precipitation to equilibrium assumes that one 1 mole of calcium will precipitate for every mole of carbonate that precipitates On this basis we can estimate a quantity X the precipitation required to restore a water to equilibrium as follows Ca X CO Ksp X is a quantitative indicator of precipitation reserve for a water X will be a small value when either calcium is high and carbonate low or when carbonate is high and calcium low It will increase to a maximum when equal parts of calcium and carbonate are present As a result this index Precipitation to Equilibrium will provide vastly different values for waters with the same saturation level Although the original Momentary Excess index was applied only to calcium carbonate scale WaterCycle extends the index to other scale forming species In the case of sulfate momentary excess is calculated by solving for X in the relationship Ca X SO X The solution becomes more complex for tricalcium phosphate 3X PO 2X Ksp The index provides a quantitative indicator of scale potential and has been used to correlate scale formation in a
64. s one pH unit above saturation Reducing the pH by 1 unit will bring the water into equilibrium This occurs because the portion of total alkalinity present as the bad actor decreases as the pH decreases A pH decrease of 1 unit will decrease the CO concentration of the water about ten fold This impacts saturation level directly by also decreasing the ion activity product tenfold So a 1 pH unit decrease will decrease the Langelier saturation index by 1 unit A 1 pH unit decrease will also decrease the saturation level AP K ten fold A negative Langelier saturation index indicates that a water is under saturated with respect to calcium carbonate calcite If the LSI is 1 0 raising the pH of the water 1 unit will increase the calcium carbonate calcite saturation level to equilibrium The 1 pH unit increase does this by increasing the CO portion of the carbonate alkalinity present ten fold The calcite saturation level increases accordingly ten times The Langelier saturation index is probably the most widely used indicator of cooling water scale potential It is purely an equilibrium index and deals only with the driving force for calcium carbonate scale formation and growth It provides no indication of how much scale CaCO3 will precipitate to bring a water to equilibrium It simply indicates the driving force for scale formation and growth in terms of pH as a master variable The Langelier saturation index is defined as Lang
65. scale inhibitors are applied as a function of a driving force for scale formation and growth e g Calcite saturation level temperature as it affects reaction rates pH as it affects the dissociation state of the inhibitor and time WaterCycle Rx allows you to develop mathematical models for the minimum effective scale inhibitor dosage as a function of these parameters driving force temperature pH and time Mathematical models for inhibitors can be developed using the Laboratory version of WaterCycle by editing water chemistry temperature and time data developed in the laboratory through field experience or both The WaterCycle Rx series is composed of the following programs e WaterCycle Rx Salesman s Edition This version of the program allows a user to select a product and obtain a dosage or dosage profile Product PRD files must be supplied for each product the salesman s version can model The program can also perform all functions of the basic WaterCycle program Dosage recommendations are incorporated into the basic WaterCycle system as an additional line of output on the tables output and as an additional graph selection in the What if modules e WaterCycle Rx Product Manager s Edition This version allows a user to input a product formulation and create a Product PRD file The program must have access to Inhibitor INH files for an inhibitor to be incorporated into a formulation The Product Manager s ver
66. sed by Customer or that Customer failed to properly follow French Creek s directions French Creek shall be entitled to be reimbursed for all out of pocket expenses plus consulting time at French Creek s then current billing rates If Customer declines maintenance at time of licensing or fails to continue maintenance services and then elects to begin or resume maintenance coverage Customer shall pay to French Creek all maintenance fees that would have been payable to French Creek if Customer had been or remained on maintenance plus an additional 10 reinstatement fee Customer may also request that French Creek provide other future modifications and enhancements under a separate agreement for such services The terms and conditions of this section state French Creek s entire responsibility to provide maintenance services hereunder 9 UNINTENDED USE Customer agrees that it will use the System as supplied by French Creek only for the purposes and in the manner set forth in this Agreement and accompanying documentation In the event that Customer breaches its responsibility under this section or if Customer is not using the System in accordance with its documentation then French Creek will have no further obligation to provide technical support or maintenance services hereunder and Customer shall not be entitled to a refund of any amount paid to French Creek In certain circumstances French Creek may also have the right to terminate this Agree
67. sion Model This method should be used to model the performance of a corrosion inhibitor versus water chemistry temperature and time Data should be selected to be at a milestone for desired results For example all data might be collected at lt 1 0 mpy lt 2 mpy lt 5 mpy or another performance target This will allow for the development of a model of dosage required to achieve the target mpy or less DEACTIVATING ANALYSIS FILES There will be times when it is desired to perform a statistical modeling of the data with the results of one or more analysis excluded from the evaluation This can be valuable in eliminating outliers to see their impact Pressing the ACTIVATE or DE ACTIVATE buttons when an analysis is on the screen ACTIVATES or DE ACTIVATES an analysis De activating does not eliminate the data from the COR file it merely excludes it from statistical evaluation LEARNING THE LABORATORY MODULES The best way to learn these modules is by using them A COR file is included for practice on modeling inhibitor performance and requirements 68 REFERENCES 1 Stumm Werner and James J Morgan Aquatic Chemistry John Wiley amp Sons 1981 2 Langelier W F The Analytical Control of Anti Corrosion Water Treatment J A W W A 8 500 1521 1936 3 Stumm Werner Investigations on the Corrosive Behavior of Waters A S C E 86 2657 4 Loewenthal R E and G v R Marais Carbonate Chemistry of Aquatic Systems A
68. sion incorporates all functions and printouts available in the basic WaterCycle program and in the Salesman s Edition of the WaterCycle Rx series e WaterCycle Rx Laboratory Edition This version allows a user to develop mathematical models for scale and corrosion inhibitors in addition to the functions of the other programs in the series Mathematical model templates are available for common inhibitors types Laboratory and or field data can be entered in forms almost identical to the regular WaterCycle chemistry input forms 17 Additional fields in the Laboratory version are time and dosage Mathematical models for an inhibitor are developed by the program using multiple regression The correlations models developed are output in the form of inhibitor INH files The goodness of fit for the data can be presented in table and graphical format The WaterCycle Rx Laboratory and Product Manager s Editions are shipped with inhibitor files for common materials such as AMP HEDP PBTC and PAA to name a basic few Inhibitor files are also available for calcium sulfate control agents calcium phosphate control corrosion inhibitors and modeling corrosion rates on mild steel Additional files are available from inhibitor s manufacturers The WaterCycle Rx Laboratory Edition includes the raw data for AA AMPS as published by Calgon in a NACE paper Correlations can be developed for dosages versus any of the WaterCycle indices any of the dat
69. te Mg 2 OH gt Mg OH Saturation level Mg OH Ksp The method used for estimating activity coefficients is a major target of criticism for most indices WaterCycle uses the mean salt activities for estimating ion activity coefficients based upon temperature and ionic strength The method is well covered in reference Truesdell and Jones 7 The use of ion pairing expands the usefulness of WaterCycle calculated saturation levels The simple indices previously described are based upon saturation levels calculated using the total ions present For example calcium carbonate indices such as the Langelier saturation index assume that all calcium is present as free calcium ions and that all carbonate is present as the unbound ion In actual waters the reactive species are present in many forms Not all of the ion measured analytically is available to react For example calcium can be bound with hydroxide sulfate carbonate and bicarbonate and unavailable for other reactions This binding or reduced availability of the reactants decreases the effective ion activity product for a saturation level calculation WaterCycle uses an ion association model to estimate the available or free ions present in the water The ion association method is well described in the literature 9019000 WaterCycle uses the free ion concentrations estimated by the ion association method in saturation level calculations The resultant saturation levels calculat
70. temperature and minimum and maximum pH values Use of this modeling capability allows a painless evaluation of scale potential and corrosivity indicators from the minimum inlet water temperature anticipated to the highest discharge temperature predicted and from the lowest pH encountered to the highest For open recirculating cooling tower systems the What If scenarios allow you to evaluate these indicators over a broad concentration ratio range The modules provide a means to evaluate the impact of pH control range choice on scale potential An overall evaluation with the What If Scenario family of modules allows you to review the water from the perspective of many complementary indices and reach conclusions tempered by your water treatment expertise The next section discusses the What If Scenario family from the perspective of functions both the ONCE THROUGH and COOLING TOWER modules have in common and based upon their own unique properties COMMON FUNCTIONS Both the ONCE THROUGH and COOLING TOWER modules require the input of a Source or Make up water analysis I n the respective modules Cooling tower scenarios also require that the water be concentrated using the Cycle module The final common thread between the scenarios is the selection of graphs for modeling Graphs can be selected using the Choose Graphs module or from the OPTIONS menu bar when a graph is displayed 35 Calcite x Sat Aragonite x Sat Anhydrite x Sat Gyps
71. terCycle products can be accessed from the FORMULARY menu by clicking on SELECT PRODUCT or from the Options Menu Bar on Table displays and graphs Clicking on the SELECT PRODUCT or NEW TREATMENT buttons elicits the following menu for product selection 100 ACUMER 3100 1100 ACUMER 5000 10096 AMP 10096 HEDP 1100 OPTIDOSE 2000 1100 OPTIDOSE 3100 _ 100 orthophosphate 110025 PAA 100 PBTC 11010 Carbon Steel AQUATREAT AR 540 _ BELCLENE 161 SELECT PRODUCT x Ca POA Inhib SiO Inhibitor CaCO3 INHIBITOR CaCO3 INHIBITOR Ca POA Inhib Ca POA Inhib corrosion inhib CaCO3 INHIBITOR STRESSED CaCO3 General Etch Ca POA Inhib CaS04 Inhibitor EE CANCER A product file PRD is associated with every menu selection Each product file contains the models for the components and the product formulation recipe Loading the product file loads the mathematical models for the inhibitors in the product into WaterCycle Once loaded they are used by the program for calculating optimum treatment rates dosages Starting with Version 6 users can select up to two products for sequential evaluation For example you can select a phosphate packahe as product 1 and a scale inhibitor phopshate control package for product 2 WaterCycle will evaluate product 1 and add the appropriate phosphate levels to the water and reclaulate all indices Then it will evaluate the dosage requirements for product 2 us
72. third party beneficiaries of this Agreement d COST OF ENFORCEMENT If either party is required to engage in legal proceedings to enforce the obligations of the other in law or in equity the prevailing party shall be entitled to reasonable attorneys fees and all related necessary and reasonable costs and expenses e SEVERABILITY In the event that any one or more of the provisions of this Agreement shall for any reason be held to be invalid illegal or unenforceable the remaining provisions of this Agreement shall be unimpaired and the invalid illegal or unenforceable provisions shall be replaced by a mutually acceptable provisions which being valid and legally enforceable comes closest to the intention of the parties underlying the invalid illegal or unenforceable provision If this Agreement or any provisions hereof are held to be invalid illegal or unenforceable under the laws of a particular jurisdiction it is the intention of the parties that all of the provisions of this Agreement shall remain in full force and effect in all other states and jurisdictions f ATTACHMENTS The terms and conditions of the attachments and Exhibits to this Agreement are incorporated herein by this reference and shall constitute a part of this Agreement as if fully set forth herein 63 g HEADINGS The section headings in this Agreement are for the purposes of reference only and shall not limit or otherwise affect any of the terms hereof h AU
73. tor in determining an effective dosage or developing a model for an inhibitor is time Time is the residence time of scale forming species in the cooling system you wish to treat The time where scale inhibition can be as short as 4 to 10 seconds in a utility condenser cooling system or extend into days for cooling towers Induction time is a term applied to the period before a water will begin to form scale In high saturation level systems the induction period can be very short In systems where a water is barely supersaturated the induction time can approach infinity Scale inhibitors have been observed to extend the induction time before scale formation or growth on existing scale substrate occurs Gill et al presented a paper at the 1984 International Water Conference which provides excellent examples of the variation of dosage requirements as critical parameters change 58 IMPACT OF HEDP CONCENTRATION ON INDUCTION TIME INDUCTION TIME seconds Thousands 0 02 0 04 0 05 HEDP CONCENTRATION mg l Figure 1 portrays the impact of HEDP dosage on induction time at constant driving force Figure 2 presents similar data for AMP 59 IMPACT OF AMP CONCENTRATION ON INDUCTION TIME 25 m o 15 10 INDUCTION TIME seconds Thousands 0 04 0 08 0 1 AMP CONCENTRATION mg l It can be seen from figures 1 and 2 that induction time increases as inhibitor dosages increases In cooling water systems scale inhibi
74. tors may function by increasing the induction time until the water has passed through the system 60 IMPACT OF CALCITE SATURATION LEVEL ON INDUCTION TIME INDUCTION TIME seconds Thousands 2 58 46 6 47 SATURATION LEVEL Ca CO3 Ksp Figure 3 demonstrates that induction time decreases with saturation level even in the presence of an inhibitor A simple mathematical description of these relationships might be modeled as Induction Time function 1 Saturation Level This models the decrease in induction time as saturation level increases The degree of supersaturation is the driving force which increases the rate at which scale will form Induction Time function Inhibitor Dosage Inhibitors extend the time before scale will form in a system by interfering with the kinetics of crystal formation and growth Rate decreases as inhibitor dosages increase Induction Time function Inhibitor Dosage 1 Saturation Level In cooling systems the inhibitors fight the driving force for scale formation and growth Inhibitors increase the induction time and interfere with reaction rates so that scale formation will not occur until the treated water has passed through the system 61 WaterCycle Rx uses more sophisticated relationships than these to model the dosage requirements for scale inhibition Additional parameters include temperature as it affects the rate of crystal formation and or growth Dosage changes with tempera
75. turation level calculations are a fifth order affair As a consequence small changes in free phosphate concentration or even smaller changes in calcium concentration have a dramatic impact on the calculated saturation level For this reason high saturation levels on the order of 100 000 or above can be observed in cooling waters treated for calcium phosphate scale control The authors experience is as follows Beware when a system is supersaturated with tricalcium phosphate A tricalcium phosphate saturation level below 100 is easily treated Most inhibitor treatments can prevent scale formation even if not specifically directed towards tricalcium phosphate pH decrease can decrease tricalcium phosphate saturation level to an acceptable level 13 pH reduction and or a tricalcium phosphate specific treatment program is recommended when tricalcium phosphate saturation level rises above the 100 to 1000 range hydroxylapatite Hydroxylapatite saturation level calculations are a ninth order affair even higher than that of tricalcium phosphate As a consequence small changes in free phosphate concentration or even smaller changes in calcium concentration have a dramatic impact on the calculated saturation level For this reason high saturation levels on the order of 100 000 or above can be observed in cooling waters treated for calcium phosphate scale control Saturation level guidelines are similar to those for tricalctum phosphate althou
76. ture can be modeled by the Arrhenius relationship D where A is a constant Ea is the activation energy R is the gas constant T is absolute temperature pH can also be included in the models pH is an important parameter to include when an inhibitor can exist in two or more forms within the pH range of use and where one of the forms is much more active as a scale inhibitor than the other s pH can also affect the type of scale that forms e g Tricalcium phosphate versus hydroxylapatite 62 DEVELOPING INHIBITOR MODELS This section describes the use of the Laboratory Edition Modules for e Inputting laboratory and field data to develop an inhibitor model e Editing inhibitor files to add special rules for handling iron e Editing inhibitor files to include a safety factor The Input Lab Data module in the LABORATORY pull down menu is used to create inhibitor INH file The module accepts initial specifications for the inhibitor e g Name Description Molecular weight and instructions for developing a model e g the Driving Force to use the modeling method New Inhibitor Data Input Pa fe ES Inhibitor Name 5 Raw Data File Aaamps COR Inhibitor Purpose Ca2 P04 2 Inhibitor OutputFie AAAMPS INH a 3 Hydrosyapatite Cab PO4 3 OH Property Modeled Scale inhibitor Dosage Molecular Weight 2500 000000 Orthophosphate asPO4 0 0000 ips 233 Property Variable Transform Lower Upper
77. um x Sat Calcium PO4 x Sat Hydroxyapatite x Sat Fluorite x Sat Silica x Sat Brucite x Sat Magnesium silicate x Sat Ferric hydroxide x Sat Siderite x Sat Strengite x Sat COMMON INDICES Langelier Index Bora u T 4 an l Leonie Ryznar Index xz CONVENIENCE GROUPS Three CONVENIENCE GROUPS have been programmed into WaterCycle to allow multiple graph selection of common groups The Common Foulants convenience group includes Calcite Silica Tricalcium phosphate and Anhydrite saturation levels The Common Indices convenience group includes the Langelier Ryznar Puckorius and Larson Skold Ratio indices The Calcium Carbonate convenience group includes Calcite saturation level Langelier Saturation Index Ryznar Stability Index and Puckorius practical Scaling Index The graphs are prepared using the profile modules which are unique to the system type and are discussed separately in the following sections 36 ONCE THROUGH WHAT IF Three scenario types can be run for once through systems The scenarios calculate the indicators of scale potential and corrosivity versus pH temperature or both The modules are called VARY TEMPERATURE VARY pH and 3D PROFILE for these scenarios Once Through What 1f Scenarios pH Selection Low pH 7 High pH 86 Evaluation pH 7 8 T emperature Selection __ __ gt _ _____E
78. ut windows will be displayed in the Cooling Tower Windows To Display and Once Through Windows To Display modules which can be accessed from the preferences menu select Windows To Display For Once Through Waters These forms allow you to customize the display of these output windows 27 Select Windows To Display For Cooling Tower Evaluations It is recommended that new users set all windows to display They can be deactivated and reactivated as desired using these forms 28 CHOOSING DATA TO PRINT You can also determine what analytical values and indices will be included in printouts by activating or deactivating individual items in the Choose Ions To Print and Choose Scales To Print forms which can be accessed from the Preferences menu Select Chemistry Items To Print lO eeerererereee 9 2 g fe 9 gi 9 9 i 29 Deposition Indicators To Print 2 9 9 9 2 9 o 9 2 9 2 9 9 genen en onen oe oo 30 CHOOSING DISPLAY SIZE The Output Size On Screen form allows you to select the number of lines form a printout that will be display on the screen This allows you to size the output window so that an entire printout can be displayed on the screen This form is also accessed through the Preferences menu Select Printout Size PRINT MODE The final setup form is rarely needed It allows the selection of either directly printing to a printer or printing indirectly by prepar
79. ute by double clicking on the SETUP EXE program icon from FILE MANAGER FILE EXPLORER or MY COMPUTER depending on your version of Windows replace A with B to install from the B drive 3 The install program will search for an existing installation You must install to the WATER directory e g CAWATER or DAWATER 4 Execute the program by clicking on the French Creek Software Icon by using the Windows RUN command or from the Windows START menu 24 Selecting Analytical Units The first time WaterCycle is run it will display a warning that default analytical input units are in affect This is a reminder to run the Input Units module which can be selected from the Preferences menu and choose the analytical reporting units used by your company ANALYTICAL UNITS SELECTION 55 P _ er mM __ _e LR Analytical units are available for almost any reporting method in use Date format can also be changed in this module You might also wish to select the ions which will be used to balance incomplete water analyses 25 Carbonate Calculations WaterCycle deals with the carbonate equilibrium in two basic ways as it cycles a water Conservation of Alkalinity or Conservation of Total Molar Carbon Carbonate based Alkalinity is conserved in systems open to the atmosphere such as cooling towers due to the free exchange of carbon dioxide with the atmosphere Molar carbbon is conserved in totally closed
80. wing an Iron Factor to be input using the Edit Coefficients module Several papers are referenced in the Appendix of this manual which outline test methods which have been used effectively to characterize the performance of inhibitors Successful correlations can also be developed based upon the field experience of water treatment personnel have worked with an inhibitor over a broad range of conditions 66 EDITING INHIBITOR FILES TO ADD SAFETY FACTORS The EDIT COEFFICIENTS module in the Laboratory menu allows 1 adding a safety factor to a model 2 adding a safety factor to account for iron and 3 phosphate content of the inhibitor if any FACTORS FOR SPECIAL CASES DE ES aam SAFETY FACTOR IRON FACTOR u Increase inhibitor dosage by A 20 to 100 general safety factor 1 20 2 00 typically is added to account for scatter in the data The Iron Factor accounts for demand for polymer by iron in the cooling water Contact French Creek Software for custom editing of models such as the combination of several discrete models into one correlation 67 CURRENT amp PAST WaterCycle Rx Models Early versions of WaterCycle Rx provides four 4 fixed basic models as well as the current custom option for developing inhibitor correlations The fixed options are included for historic perspective The same models can be setup using the current custom option forms Older models are updated to the custom format when imp
81. x Ryznar Stability Index and Puckorius or Predictive Scaling Index are well documented Values calculated by WaterCycle for these indices should be very close to those calculated using normal methods Guidelines for these indices are covered in their respective sections of this manual It should be noted that these indices are limited to calcium carbonate scale potential They are based upon total calcium and total alkalinity present and may be of limited usefulness in high TDS waters for this reason The do not account for ion pairing It is recommended that these indices be used as points of reference only and that the more rigorous saturation level for calcite be adopted especially in high TDS waters 14 WaterCycle COLOR CODING Graphs produced by WaterCycle are color coded as an aid in interpreting them This section discusses the meaning of the colors Saturation Level and Simple Scale Indices RED Red signifies a definite problem prediction Corrective action such as treatment pH adjustment or concentration ratio decrease blowdown should be taken to eliminate or alleviate the problem Red signifies loss of control in TREATED SATURATION LEVEL PROFILES MAGENTA Magenta purple signifies that a problem is highly likely Some systems might be able to carry the degree of supersaturation indicated by magenta without deposition occurring Most system will scale if operated in the Magenta range without treatment YELLOW Yellow s
82. y this warranty and indemnity shall not apply if the basis for the infringement claim is due to the System being used in conjunction with software not supplied by French Creek hereunder or which differs in any way from the software or equipment configuration specified in the documentation for use with the System This section states French Creek s entire liability concerning allegations that French Creek lacked the right to license the System hereunder The terms and conditions of this section shall survive any termination of this Agreement 7 CONFIDENTIAL INFORMATION Customer acknowledges that the System and accompanying documentation constitute valuable and proprietary property of French Creek Customer understands and agrees that French Creek may suffer irreparable harm in the event of any unauthorized disclosure of any portion of the System and or its accompanying documentation which may substantially diminish the value of such System and documentation to French Creek Therefore Customer agrees not to disclose any portion of the System or accompanying documentation without the prior written consent of French Creek except that Customer may disclose such materials a to employees of Customer who have a need to be familiar with the operation of the System or its accompanying documentation b to any governmental agency with supervisory authority over Customer or pursuant to compulsory legal process or c to others in a strict confidential rel
83. ycle Rx license is subject to the following conditions a Customer acknowledges that the software and other technical data licensed hereunder are subject to export 71 controls imposed on Customer and French Creek by the provisions of the United States Export Administration Act of 1979 as amended and that the software is exported under a General Export License designation GTDR and that the documentation is exported under a General License designation GTDA Customer certifies to French Creek that neither the technical data in the form of software or manuals nor the direct product thereof is intended to be shipped either directly or indirectly to Country Groups Q S W Y or Z nor Afghanistan or the Peoples Republic of China without further compliance with the Validated License requirements of the Office of Export Administration United States Department of Commerce Customer agrees to use this technical data only at authorized destinations and Customer will not knowingly permit exportation or transshipment in violation of the above law and regulations thereunder Customer agrees to indemnify and hold French Creek harmless from any and all costs damages fines or other expenses incurred by French Creek by reason of Customer s violation of these representations of Customer b Each copy of the System may only be used by Customer on one equipment work station as defined in the System documentation at any one time Customer may not use

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