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The design of a zero-effluent discharge system for Westcoast Energy inc.’s Fort Nelson Gas Plant 1995

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T H E D E S I G N O F A Z E R O - E F F L U E N T D I S C H A R G E S Y S T E M F O R W E S T C O A S T E N E R G Y INC. 'S F O R T N E L S O N G A S P L A N T by J E A N - P H I L I P P E B E C H T O L D B . S c , The University Of Western Ontario, 1993 A THESIS S U B M I T T E D I N P A R T I A L F U L F I L L M E N T OF T H E R E Q U I R E M E N T S F O R T H E D E G R E E OF M A S T E R O F A P P L I E D S C I E N C E in T H E F A C U L T Y O F G R A D U A T E STUDIES (Department of Civ i l Engineering) We accept this thesis as confonning to the_required standard T H E U N I V E R S I T Y OF B R I T I S H C O L U M B I A June 1996 © Jean-Philippe Bechtold, 1996 In presenting this thesis in partial fulfilment of the requirements for an advanced degree at the University of British! Columbia, I agree that the Library shall make it freely available for reference and study. I further agree that permission for extensive copying of this thesis for scholarly purposes may be granted by the head of my department or by his or her representatives. It is understood that copying or publication of this thesis for financial gain shall not be allowed without my written permission. Department of cC^^u Er^Z- The University of British Columbia Vancouver, Canada Date J grsj <g DE-6 (2/88) ABSTRACT This project was initiated by Westcoast Energy Inc. (Westcoast) to examine the feasibility of transforming their Fort Nelson Gas Plant (FNGP) into a zero-effluent discharge (ZED) facility. Water flow and water chemistry data were collected at the plant. The resulting data set was used to identify water leaks in the existing distribution network, as well as to identify methods of optimizing water use at this facility. Designs for implementing a Z E D protocol at the F N G P were then developed and subsequently evaluated with a computer simulator. A total of 18 Z E D models were constructed using reverse osmosis (RO) membranes, nanofilters and other Z E D technology. The final disposal mechanism in 10 of the 18 scenarios was a brine concentrator - spray dryer (BCS) assembly, which reduced all remaining wastewater into a solid waste. In the other 8 Z E D designs, final concentrates were disposed of in a deep well. The best deep well configuration was a 1-stage R O filter; the necessary equipment, excluding the deep well , would cost an estimated $101 700 US dollars. The best B C S scenarios were a 1-stage R O and a BCS-only models; they would cost around $1.61 and $1.79 mill ion US dollars, respectively. A step by step approach by which the F N G P can be transformed into a Z E D facility is detailed in Chapter 8.0 of this report. While it is possible to implement a Z E D program at the F N G P , there are consequences to this course of action which need to be considered. The most important is final waste management. Regardless of whether a deep well or a B C S unit is used, either system wi l l have to be built and operated in such a way that the final waste products produced by the Z E D treatment train do not migrate off-site, as this action would violate the Z E D principle. Once a Z E D program is initiated, wastewater and/or waste solids produced at the F N G P wi l l no longer disappear with the F N R ; they wi l l remain on-site indefinitely. ii TABLE OF CONTENTS Abstract i i List of tables vi List of figures viii Acknowledgements ix 1.0 I N T R O D U C T I O N 1 2.0 B A C K G R O U N D 2.1 Gas Plant Operations 2.1.1 G e n e r a l 7 2.1.2 Fort Nelson Gas Plant 7 2.2 F N G P Water System 2.2.1 Liquid phase 8 2.2.2 Vapour phase 11 3.0 A V A I L A B L E R E C Y C L I N G T E C H N O L O G Y 3.1 Distillation 18 3.2 Ion-exchange 18 3.3 Membrane Filtration 3.3.1 Ion selective separation 19 3.3.2 Water permeable membranes 21 3.3.3 Reverse osmosis vs. electrodialysis 23 3.3.4 R O membrane selection 32 3.4 Brine Disposal 33 3.5 Conclusion 35 4.0 M E T H O D O L O G Y 4.1 Analysis of the Existing Water Distribution System 4.1.1 Flow data 42 4.1.2 Chemical data 42 4.2 Selecting the Appropriate Recycling Technology for the F N G P 44 4.3 The Computer Simulator 4.3.1 Basic consttuction 45 4.3.2 Z E D components 46 4.3.3 Parameter values 47 5.0 A N A L Y S I S O F T H E E X I S T I N G W A T E R S Y S T E M 5.1 Results 5.1.1 Water balances 50 5.1.2 Mass balances 50 iii T O C (con't) 5.0 A N A L Y S I S O F T H E E X I S T I N G W A T E R S Y S T E M (con't) 5.2 Discussion 5.2.1 Data quality 51 5.2.2 System optimization 54 5.3 Changing to a Z E D System 59 5.4 Conclusion 60 6.0 R E C Y C L I N G T E C H N O L O G Y F O R T H E F N G P 6.1 Re-evaluation of the Literature Review 88 6.2 Available Options 89 6.3 Conceptual Z E D Designs 6.3.1 B ack-end models 91 6.3.2 Composite discharge designs 92 7.0 D E S I G N E V A L U A T I O N 7.1 Simulator Performance 95 7.2 B C S Designs 7.2.1 Composite discharge models 96 7.2.2 Back-end solutions: ion-exchange vs. nanofiltration 96 7.2.3 Best of the back-end ion-exchangers 98 7.2.4 Conclusion 101 7.3 Deep W e l l Configurations 7.3.1 Composite discharge designs 102 7.3.2 Back-end solutions: ion-exchange vs. nanofiltration 102 7.3.3 Best of the back-end ion-exchangers 102 7.3.4 Conclusion 103 7.4 Evaluation S ummary 104 8.0 Z E D I M P L E M E N T A T I O N A N D I M P L I C A T I O N S 125 9.0 P O T E N T I A L L I M I T A T I O N S 9.1 Non-Representative numbers 9.1.1 Flow data 130 9.1.2 Chemical data 130 9.2 Sample Variability 9.2.1 Water data 131 9.2.2 Chemical data 131 9.3 Computer Model 132 9.4 Z E D Evaluation Process 133 9.5 Conclusion 134 iv TOC (con't) 10.0 C O N C L U S I O N S 136 11.0 R E C O M M E N D A T I O N S 138 References 139 Appendix A - Water flow data 146 Appendix B - Water balance equations and assumptions 186 Appendix C - Water chemistry data 194 Appendix D - Mass balance equations and assumptions 207 Appendix E - Equations used in the computer simulator 213 Appendix F - Simulator summary sheets 268 Appendix G - Cost estimates 278 v LIST OF TABLES Table 3.1: A comparison of the inherent advantages and disadvantages of reverse osmosis (RO), electrodialysis (ED) and electtodialysis reversal (EDR) 36 Table 5.1: A water balance of the Fort Nelson Gas Plant based on its individual operating units 63 Table 5.2: A water balance of the Fort Nelson Gas Plant based on the different types of water used at the facility 70 Table 5.3 A summary of treated water losses from the Fort Nelson Gas Plant 74 Table 5.4: A mass balance on the front-end softening system 75 Table 5.5: A mass balance on the lime ponds 76 Table 5.6: A mass balance on the boilers 77 Table 5.7: A mass balance on the sulphur plant 78 Table 5.8: A mass balance on the polishing pond 79 Table 5.9: A comparison between water flow readings from January 1995 and overall averages 80 Table 5.10: Water balances on the raw water storage tank and front-end softeners (FESs) using metered and calculated inflow and outflow volumes from the FESs 82 Table 5.11: Recalculated mass balance on the FNGP's front-end softening system 83 Table 5.12: Recalculated mass balance on the FNGP's lime ponds 84 Table 5.13: Changes that occurred in selected areas of the Fort Nelson Gas Plant's water system before and after water observed to be escaping from the effluent treatment plant was recovered 85 Table 5.14: Selected water flows in the Fort Nelson Gas Plant's water distribution network with and without 8 psi steam reuse 86 Table 5.15: The average inlet gas profile for January 1994 at the Fort Nelson Gas Plant 87 Table 6.1: A chemical comparison of the treated water and Fort Nelson River (FNR) discharge flows 93 Table 7.1: Comparison of 10 selected B C S Z E D designs 106 Table 7.2 Changes in R O and B / C feedwater flows, calcium pretreatment demands and product water quality, in the 1-stage R O , 2-stage R O and BCS-only back-end, B C S , ion-exchange configurations, triggered by given alterations in raw water and effluent plant outflow chemistry 108 vi LIST OF TABLES (con't) Table 7.3: Changes in treated water quality, in the 1-stage R O , 2-stage R O and BCS-only back-end, B C S , ion-exchange configurations, ttiggered by given alterations in raw water and effluent plant outflow chemistry I l l Table 7.4: Comparison of 8 selected deep well Z E D designs 113 Table 7.5: Changes in R O feedwater flow, calcium pretreatment demands and product water quality, in the 1-stage and 2-stage R O back-end, deep well , ion-exchange configurations, triggered by given alterations in raw water and effluent plant outflow chemistry 115 Table 7.6: Changes in treated water quality, in both the 1-stage and 2-stage R O back-end, deep well, ion-exchange configurations, triggered by given alterations in raw water and effluent plant outflow chemistry 117 Table 9.1: Changes to the configuration of the back-end, B C S , 1-stage R O , ion-exchange design with various flow alterations , 135 vi i LIST OF FIGURES Figure 1.1: Water balance at the Fort Nelson Gas Plant before and after ZED implementation .. .5 Figure 1.2: Salt balance at the Fort Nelson Gas Plant before and after ZED implementation 6 Figure 2.1: An illustration of Westcoast Energy Inc.'s operations in British Columbia 13 Figure 2.2: General layout of the Fort Nelson Gas Plant 14 Figure 2.3: An illustration of gas processing flows at the Fort Nelson Gas Plant 15 Figure 2.4: A simplified illustration of the Fort Nelson Gas Plant's water system 16 Figure 2.5: A simplified illustration of the Fort Nelson Gas Plant's steam system 17 Figure 3.1: Typical operating total dissolved solid (TDS) concentrations for different desalination technologies 37 Figure 3.2: An illustration of the electrodialysis process 38 Figure 3.3a: Flows through an EDR stack when elecuicity travels from right to left 39 Figure 3.3b: Flows through an EDR stack when electricity travels from left to right 39 Figure 3.4: Pore size distribution in three types of water permeable membranes 40 Figure 3.5: An illustration of reverse osmosis (RO) filtration 41 Figure 4.1: A simplified diagram of the water distribution system at the Fort Nelson Gas Plant 49 Figure 6.1: A graphic representation of the available ZED options 94 Figure 7.1: An illustration of the projected flow patterns in a composite discharge, reverse osmosis Z E D configuration 119 Figure 7.2: An illustration of the changes in equipment and flow patterns in a given ZED system using nanofiltration instead of ion-exchange softening 120 Figure 7.3: An illustration of the projected flow patterns in a back-end, BCS-only ZED configuration 121 Figure 7.4: An illustration of the projected flow patterns in a back-end, reverse osmosis ZED configuration 122 Figure 7.5: A simplified illustration of a 1-stage RO, BCS ZED system.. 123 Figure 7.6: A simplified illustration of a 2-stage RO, BCS ZED system 124 viii ACKNOWLEDGEMENTS First and foremost, I would like to thank Wayne Soper for first hiring me as a summer student and then later arranging for Westcoast Energy Inc. to sponsor my thesis. I am also indebted to Bruce Kosugi , E d Lee, Shang Su and Lorraine Michot for their assistance. A s for the staff at U B C , I would like to thank J im Atwater for his guidance and insight, Don Mavinic for his helpful comments, and Pat Sheehan for making my time at U B C easier and more enjoyable. On a more personal note, I owe a great deal to my family. They have always been very loving and supportive. A special mention to my father, if it were not for his generosity, I would never have been able to come out to Vancouver. He is an amazing individual, and I am honoured to have him as my dad, even i f he does give me a little too much unsolicited advice. I am also grateful to Wayne Evans and Joanna McGrenere for providing me with a constant source of comic relief and inspiration, and to my step-mother, Raymonde Pommier-Bechtold, as well as to Steve Banks, Sheilah Marans and Elvira Latts, for typing up several sections of my thesis. I am eternally indebted to Belinda Fireman who helped me weather many a storm and guided me through to brighter days. Finally, using words borrowed from Nelson Mandela, "...I have discovered the secret that after climbing a great hi l l , one only finds that there are many more hills to climb. I have taken a moment here to rest, to steal a view of the glorious vista that surrounds me, to look back on the distance I have come. But I can rest only for a moment... for my long walk is not yet ended." ix 1.0 INTRODUCTION A zero-effluent discharge (ZED) facility, as defined by some, should not release any waste products into the environment. There would be no wastewater discharges, no atmospheric emissions and no solid waste output. The plant would essentially exist as closed system. There are few such facilities in existence, due to the cost, complexity and possible impracticality of a completely closed system. Z E D is, as a result, more commonly used to describe a facility which does not release any wastewater into its surroundings. Incentives for implementing a Z E D program can include a reduction in overall operating costs, improved environmental quality and/or regulatory compliance. Westcoast Energy Inc. (Westcoast) initiated the Z E D project as a potential alternative to upgrading the current effluent tteatment facilities at its Fort Nelson Gas Plant (FNGP), as wi l l be required by stricter environmental guidelines. B y eliminating the wastewater discharge stream now released to the Fort Nelson River (FNR), the F N G P w i l l be able to operate independent of British Columbia's wastewater legislation. The feasibility of implementing a Z E D system at the F N G P is, however, bound by two initial conditions: 1) Westcoast has stipulated that while domestic wastewaters are part of the F N R discharge and wi l l , as a result, have to be included in any Z E D program, no recycled water w i l l enter the domestic system; it wi l l continue to draw fresh water from the plant's raw water reservoir. and 2) Most of the water used in the operational sections of the plant is softened water. B y condition (1), domestic wastewater wi l l become a source of water for the plant (Fig. 1.1). If operational water losses do not exceed domestic wastewater input, the Z E D project is doomed to 1 fail. The surplus of domestic wastewater would necessitate a liquid discharge from this facility - a violation of the founding principle of a Z E D system. It wi l l therefore be impossible to eliminate the F N R discharge i f the plant's domestic wastewater production proves to be greater than its operational water losses, so long as recycled water is not used in the domestic system. While boundary condition (2) does not affect the FNGP's water balance, it w i l l still have profound effects on the Z E D project. A l l of the chemical contaminants snipped from raw water now used in the operational sections of this facility are currently discharged along with the plant's wastewater to the F N R . When this wastewater is recycled, as w i l l be the case in a Z E D program, these elements w i l l be returned to the head of operations. Here, they wi l l be joined by additional salts contained in the raw and domestic waters needed to replace process water losses. To maintain a chemical balance, some salts and other contaminants wi l l have to be drained from the Z E D treatment train (Fig. 1.2). Otherwise, these materials wi l l accumulate within the water distribution network with destructive results. Although adopting a Z E D framework w i l l release the F N G P from some regulatory guidelines, the ability to implement such a program may be limited by both the size of this facility's domestic wastewater output and the continued production of a salt brine or solid waste from any Z E D treatment system. Optimizing the FNGP's water distribution network is likely to increase the viability of a Z E D program, as it w i l l minimize the limitations imposed on this project by both boundary conditions. For example, the amount of brine or solid waste ultimately produced by a Z E D treatment train is directly proportional to the volume of softened water lost from the plant. Tightening up the distribution system and reducing process water losses wi l l shrink the demand for make-up water. Less raw water w i l l then need to be imported from the raw water reservoir and fed into the front- end softeners (FESs). A s feedwater volumes to the FESs drop, so to w i l l the mass of contaminants discharged from these vessels. Minimizing water loss in the operational sections of the plant wi l l therefore limit Z E D waste output by reducing incoming raw water flow and waste generation rates in the FESs. 2 Increasing the efficiency of the domestic system is similarly important to the success of the Z E D project. A s previously stated, domestic wastewater production rates must be smaller than operational water losses as a prerequisite to initiating a Z E D program. On one hand, this condition restricts process system optimization, in that one does not want to reduce process water losses to the point where they are less than the domestic output. A t the same time, it also implies that minimizing domestic wastewater production wi l l theoretically permit a greater amount of process optimization and increase the probability of fulfilling the prerequisite flow regime (i.e. domestic wastewater production < operational water losses). In addition to these benefits, network optimization, on the whole, w i l l help to minimize the cost and complexity of the required Z E D freatment train. Reducing process water losses wi l l , as previously stated, reduce the mass of contaminants contained in the F N R discharge by limiting their production in the FESs. Similarly, reusing relatively uncontaminated wastewaters, instead of releasing them into the effluent system, wil l reduce the volume of F N R discharge. Since the goal of the Z E D project is to eliminate the release of wastewater to the F N R , the FNGP' s discharge stream wi l l ultimately need to be cleaned and recycled back into the plant. Reducing the volume and level of contamination of this wastewater, as achieved through system optimization, can only help to simplify this task. Increasing the efficiency of the existing water network is, therefore, a key step in establishing a cost effective Z E D program at the F N G P ; it wi l l lead to a smaller, less contaminated final plant outflow which wil l be easier to recycle and produce less final solid waste than the current F N R discharge stream. In order to identify i f operational water losses at the plant are greater than its domestic output, as well as where water is now lost from the facility, flow diagrams and water balances were consti'ucted. Plant waters were then analyzed to determine which of the escaping su'eams could be directiy reused and which others would require pretreatment before reuse. Conceptual Z E D designs, which detail the configuration of the F N G P as a Z E D facility, were developed by combining information from available literature with the assembled flow diagrams and collected 3 water chemistry data. Computer modeling was used to evaluate the efficiency of each design. The process by which all of this work occurred is discussed in the following report, starting with a brief description of the F N G P , a review of the current literature and an outline of the methodology used in this study. Later chapters detail an analysis of the plant's existing water distribution network, the appropriate recycling technology and the best Z E D configurations available to this facility. How a Z E D program should be implemented, together with this project's potential limitation, conclusions and recommendations, are all examined in the final sections of this document. 4 Before ZED implementation Escaping water i _ Plant Operations Raw water / reservoir \ K Domestic water system Wastewater Fort Nelson River After ZED implementation Raw water reservoir Escaping water A Plant Operations Z E D system Domestic water system Surplus Fort Nelson River Figure 1.1: Water balance at the Fort Nelson Gas Plant before and after Z E D implementation. Before ZED implementation Raw water > reservoir Water Plant Softeners Operations 7 F o i l Nelson River Domestic water system After ZED implementation Raw water reservoir \ Water Plant Softeners Operations 7 Domestic water system Salt brine or Sol id waste Figure 1.2: Salt balance at the Fort Nelson Gas Plant before and after Z E D implementation 6 2.0 BACKGROUND 2.1 Gas Plant Operations 2.1.1 General Natural gas reserves are rarely pure methane. They generally contain a mixture of water, carbon dioxide, hydrogen sulphide and methane (Medici 1974, Ikoku 1984). Natural gas containing high levels of carbon dioxide and hydrogen sulfide is referred to as "sour" or "high acid" gas (Medici 1974, Ikoku 1984). Conversely, "sweet" gas is virtually free of pollutants (Medici 1974, Ikoku 1984). Normally raw field or production gas is dehydrated close to the well head. The remaining contaminants are removed downstream at processing plants. Production gas may also contain various heavier hydrocarbons, including ethane, propane, and butane; such gas being referred to as wet gas (as opposed to dry gas) (Medici 1974, Ikoku 1984). Processing facilities remove these liquids in addition to other undesirables, producing dry sweet sales gas. In British Columbia, most natural gas processing is undertaken at 5 major plants, including the FNGP (Fig. 2.1), all of which are owned and operated by Westcoast Energy Inc.. As shown in Figure 2.1, field production is moved through a myriad of gas gathering pipelines to these 5 major processing facilities, and sales gas is then transported via Westcoast's major trunk pipeline system to markets in British Columbia and the U.S. 2.1.2 Fort Nelson Gas Plant As field gas enters the FNGP, which itself is illustrated in Figure 2.2, it first passes through a liquid separator where liquid hydrocarbons and the remaining water are isolated from the gas (Fig. 2.3). At this point, the gas stream typically contains 87 % methane, 12 % carbon dioxide and 1 % hydrogen sulphide by volume (E/F Manual). The carbon dioxide and hydrogen sulphide are stripped from the gas using either diethanolamine (DEA), monoethanolamine (MEA), potassium carbonate (KCO3) or combination thereof (E/F and C/D Manuals). The "scrubbed" gas, although free of carbon dioxide and hydrogen sulphide, is now saturated with water from the stripping 7 solutions. This water is removed in dehydrators, and the sweet dry gas is released into the sales pipeline. Water trapped by the dehydrators drains to the flare pits for disposal. The D E A , M E A and K C O 3 solutions are not used on a "once-through" basis. Contaminated liquids are regenerated by steam cleaning (E/F and C/D Manuals). Carbon dioxide and hydrogen sulphide are leached out of the spent stripping solutions by counter-current steam flows (Fig. 2.3). The contaminated steam exits the gas processing trains and travels to a sulphur recovery unit. Hydrogen sulphide is a poisonous gas which cannot, under current government regulations, be freely released into the environment. Hydrogen sulphide extracted from sour gas is changed into elemental sulphur by reacting it with sulphur dioxide. This transformation, known as the "Claus" process, typically recovers 98 % of the incoming hydrogen sulphide (S/P Manual). Remaining hydrogen sulphide is burnt to sulfur dioxide and released along with all of the carbon dioxide and water contained in the vapor stream evolved when regenerating the D E A , M E A and K C O 3 solutions (Fig. 2.3). In simple terms, gas processing at the F N G P consists primarily of snipping liquid and gaseous contaminants from incoming sour gas to produce sweet sales gas, the conversion of hydrogen sulphide to elemental sulphur, and the atmospheric release of carbon dioxide, low levels of sulphur dioxide and steam. 2.2 FNGP Water Svstem Water at the F N G P is used for processing and power generation, as well as for cleaning and domestic purposes. Depending on temperature and pressure, it exists as either a liquid or a gas. 2.2.1 L iqu id Phase A l l of the water required by the plant originates from either the Fort Nelson River (FNR) or Burger creek (a minor water flow used in the spring and summer months). Water from either source initially travels to the raw water reservoir. From the reservoir, it is pumped, as required, to 8 a storage tank closer to the facility (Fig. 2.4). Water passes into the plant in one of three different flow systems: i) Cleaning water is drawn directly from the tank and travels through the plant's "raw water" piping. ii) Water destined for domestic use moves from the tanks through two activated carbon filters; it is then chlorinated and dispersed throughout the plant in the domestic system. iii) The remaining water by-passes the domestic treatment train and flows into a water softening system; it is henceforth called tteated water. Dirty cleaning and domestic waters are released into the effluent system, which ttansports them to the effluent treatment plant (Fig. 2.4). A l l of the surface drains within the F N G P also drain to the effluent facility. Rainwater, collected in a series of ditches and culverts, does not enter the plant's water network. It is directed off-site, unless it has been contaminated by an on-site spill (Plant Modifications 1994). If rainwater does become contaminated, then it is pumped to the effluent plant for treatment. Similarly, polluted groundwater around the facility is treated at the effluent plant (Plant Modifications 1994). In general, very little "outside" water (i.e. precipitation and/or groundwater) enters the FNGP's water network, and cleaning & domestic waters ttavel through separated pipelines until they mix in the effluent system. Treated water produced by the front-end softeners (FESs) similarly remains isolated from the other water systems. Most treated water is used as boiler-feed make-up or dilutant for the natural gas snipping solutions (Fig. 2.4). Remaining treated water is used to regenerate the FESs, backwash the domestic filters or for cleaning equipment too sensitive to be washed with raw water. Spent regeneration and backwash waters drain to the lime ponds, while dirty cleaning water goes to the effluent plant. 9 Four of the 6 natural gas processing trains at the F N G P use treated water to replace water lost from the natural gas snipping solutions (i.e. regeneration steam and flare water - F ig . 2.3) (E/F Manual). The other 2 processing ttains replace their lost water with water from the condensate return line (Fig. 2.4). Regardless of their origins, waters headed to "Process" are, for the most part, lost from the water network upon arrival. They are either eventually released to the atmosphere via the thermo-oxidizer or vapourized in the flare pits (Fig. 2.4). A small volume of flare water may remain in the pits not having evaporated during flaring. This residue wi l l drain into the effluent tteatment plant. In general, water which comes into direct contact with natural gas does not cycle into any other patt of the water network, except from the small volumes of flare water draining to the effluent treatment facility. Contaminants carried into the plant in the gas stream can, however, be transported down to the effluent plant in waters used to clean process vessels. Boiler feedwater (BFW) is a combination of treated water and returned condensate (Fig. 2.4). It is pumped into the 3 boilers and various vessels within the sulphur plant. A small volume of B F W drains from the boilers and the sulphur plant to control contaminant concenQ-ations within the steam system, while the remaining water is vapourized and released into the steam system. Blowdown waters collect in the lime ponds. The lime ponds receive wastewater from, as indicated, the boilers and the sulphur plant, as well as from the domestic filters, the FESs and several treated water drains within the F N G P (Fig. 2.4). The effluent plant, on the other hand, mainly receives domestic sewage, dirty cleaning water and a tiny amount of water from the flare pits. While the lime ponds are nothing more than collection basins, the effluent plant is comprised of a 20-day stabilization pond, a 5-day activated sludge tank and 3 clarifiers (E/P Manual). Lime pond and effluent plant outflows are combined in a mixing tank, flow through a 1-day retention pond (referred to as the "polishing" pond), and are released to the F N R . 10 Raw water entering the F N G P is either directly used for cleaning, is filtered, chlorinated and used for domestic purposes, or is softened and called treated water. Spent cleaning and domestic waters are collected, treated and released to the F N R . Some tteated water, following its use as either cleaning, regenerating or blowdown water, is also collected and discharged to the F N R . The rest of the treated water appears to be lost through the flare pits and thermo-oxidizer. 2.2.2 Vapour Phase Some of the tteated water produced by the FESs mixes, as previously indicated, with condensate, forming B F W . Most of the B F W is pumped into the boilers, although some of it goes into the sulphur plant (Fig. 2.4). A l l of the B F W is transformed into steam, regardless of its destination. The boilers produce 450 psi steam, which is used to power elecuical turbines, high pressure pumps and gas blowers (Fig. 2.5). B F W going to the sulphur plant changes to either 150, 45 or 15 psi steam, depending on where it was vapourized in the sulphur recovery ft-ain. Petrosul, a neighboring firm, purchases a small quantity of 150 psi steam. The rest of it is used to drive the sulphur plant's air intake blowers. Gas blowers, electrical turbines and high pressure pumps all release 45 psi steam (Fig. 2.5). Combined with the 45 psi steam originally created in the sulphur plant, most of this water vapour travels to process train reboilers. Here it heats clean natural gas snipping solutions to their boiling point. Steam produced from the boiling stripping liquids is used for self-cleaning (i.e. steam from uncontaminated solution is used to clean spent liquor) and released to the sulphur plant. Treated water and/or condensate is imported into "Process", as previously described, to replace these water losses. With its heat energy transferred to the snipping liquors, the 45 psi steam condenses and leaves the reboilers as a liquid. Forty-five psi steam not destined for process equipment is used for heating elsewhere in the plant. It eventually cools and condenses. Condensed steam is collected and returned to the B F W 11 tank (Fig. 2.5). The only exception is a small amount of 45 psi steam blown through the deaerators, wherein its pressure drops to 8 psi. The emerging 8 psi steam is vented to the atmosphere. Five and 150 psi steam created in the sulphur plant are used therein and collected as condensate (Fig. 2.5). It is similarly returned to the head to the plant with the rest of the condensate. The steam system at the F N G P is already quite efficient. As each steam loop remains isolated within the natural gas processing and sulphur plant equipment, there is no opportunity for contamination of these high quality waters. As a result, most of the water pumped through the steam system is reused. The need for B F W make-up, however, indicates the presence of steam leaks within the facility, possibly beyond the boiler and sulphur plant blowdowns and Petrosul outlet previously identified. Overall, water, existing as either a liquid or a gas, is used for a number of puiposes at the F N G P , ranging from cleaning to power generation. A large proportion of water in the system is reused. Never the less, the demand of treated water make-up suggests that there are leaks in the operational water loops. A l l of the missing water may be escaping through the thermo-oxidizer, the flare pits and the steam outlet to Petrosul. This premise can, however, only be evaluated with a more thorough investigation of the plant's water network, hence the inclusion of a system diagnostic in the Z E D project. 12 Figure 2.1: A n illustration of Westcoast Energy Inc.'s operations in British Columbia 13 Alaska Highway 14 o S « — <U o3 00 £ £ 3 T 3 a a • r H 6 c o U O > 00 CN ffi <N o u CN o oo CD "2 o '•3 a o •a '•3 JJ ™ x o + 03 CN CD O S 5 •a a S '"2 s II II II II % K <N O ̂  " 0,1 U ffi oo ffi oo O c 00 o II <N O 'S oo CD o > 6 < t CN CN O O <N CN Uffiffi 00 T 3 CD t - i CD > O o CD 3 si T 3 '3 c 03 on 03 O e o 00 t i o CD 03 on O bo c on O o oo C 03 t 3 on 3 . r H C < fN <U S- S 15 Fort Nelson River (fall & winter) Burger creek (spring & summer) ^ Raw water tank ^ Raw water cleaning I I Wastewater Effluent Plant Domestic system 1 1 Water softeners Regeneration waters Treated water tanks Wastewater -\ Cleaning water Domestic filter backwash Remaining , „ „ F i a r e w a t e i H G a s Processing 3 Spent regeneration & blowdown waters Boiler feedwater tank Condensate Boilers & Sulphur Plant 1 Blowdown Discharged to Fort Nelson River Wastewater 1 Figure 2.4: A simplified illustration of the Fort Nelson Gas Plant's water system. 16 c Treated water tanks i — Condensate »^Boi ler feedwater tank Sulphur Plant t I 0 Various vessels f 150 psi steam y T 15 psi steam 45 psi steam A i r blowers T 5 psi steam i i Condensors Boiler feedwater 1 Boilers 450 psi steam • I I t Turbines High pressure pumps 45 psi steam Gas blowers Steam ttacing & Preheaters Condensate J Reboilers Deaerators T 8 psi steam Atmosphere Figure 2.5: A simplified illustration of the Fort Nelson Gas Plant's steam system. 17 3.0 AVAILABLE RECYCLING TECHNOLOGY Reusing process wastewaters and/or secondary domestic effluent is not an uncommon practice, even at power plants and other steam generating facilities (e.g. Abdullaev et. al. 1992, Pankratz & Johanson 1992, Bowl in & Ludlum 1992, Pierce & Sbei 1993, Strauss 1994, Strauss 1995). The recycling systems tend to involve one or more of the following principles: distillation (Brew & Blackwel l 1991, Bowl in & Ludlum 1992, Strauss 1994), ion exchange (Kalinske et. al. 1979, Egozy et. al. 1980, Abdullaev et. al. 1992, Bowlin & Ludlum 1992), and/or membrane filtration (Pankratz & Johanson 1992, Bowl in & Ludlum 1992, Strauss 1994, Strauss 1995). 3.1 Distillation Distillation uses heat energy to produce high quality steam from the contaminated wastewater (Kalinske et. al. 1979, Wood 1987, Parekh 1991). The steam can either be reused directly, or first cooled to a liquid. The volume of the remaining waste stream is significantly reduced, i f not completely transformed to a solid. This relatively energy intensive process is generally most efficient and cost-effective for waters with total dissolved solid (TDS) levels above 10 000 mg/L (Fig. 3.1). 3.2 Ion-exchange Ion-selective resins are the backbone of the ion exchange process (Kalinske et. al. 1979, H i l l & Lorch 1987, Parekh 1991). These resins, or beads, are coated with relatively inert ions. A s wastewater travels through an ion exchanger, unwanted ionic species are adsorbed, and replaced with more process friendly ions. The influent water is now clean and ready for reuse. The resins themselves eventually become saturated with contaminants. They are then regenerated, and the process starts anew. The optimal TDS range for ion exchanger is generally between 100 and 800 mg/L (Fig. 3.1). 18 3.3 Membrane Filtration Unlike either of the previous techniques, membrane filti'ation involves neither heat energy nor ion replacement. A s the name implies, undesirable elements in the wastewater are isolated using membrane filters (Kalinske et. al. 1979, Applegate 1984, A W W A 1989, Huang & Koseoglu 1993). The configuration of the filter determines what elements are removed, and which others are not (Applegate 1984, A W W A 1989, Cartwright 1991). Membrane filtration has been found to work best with wastewater TDS concentrations between 100 and 10 000 mg/L (Fig. 3.1). There are, however, two general classes of membrane filters; those that are ion selective, and others which are water permeable (Kalinske et. al. 1979, Applegate 1984, A W W A 1989, Cartwright 1991, Huang & Koseoglu 1993). Due to the specificity of their membranes, the two processes are fundamentally different from one another. Each one has its own inherent advantages and disadvantages. 3.3.1 Ion selective separation Ion selective separation, more commonly referred to as electrodialysis (ED), uses filters which are designed to allow either only cation or only anion passage through the membrane (Kalinske et. al. 1979, Applegate 1984, Solt & Foster 1987, A W W A 1989). In its most basic application, cationic and anionic filters are alternately stacked between an anode and a cathode (Fig. 3.2). Each cationic/anionic group is called a cell, and contained within each cell are two open areas bounded by the membranes. Water, flowing parallel to the filters, fills these spaces. When a direct current is applied to the system, cations and anions in solution move toward the cathode and anode, respectively (Fig. 3.2). With alternating cationic/anionic filters, water in one compartment w i l l be drained of its ionic contaminants, while water in the neighbouring space wi l l become increasingly contaminated. The clean and dirty waters are then collected separately as they exit the cells. Several adaptations have been made to the basic E D configuration in attempts to either increase the robustness of the system or to improve effluent water quality. Sealed-cell electrodialysis, 19 which involves sealing each cationic/anionic membrane pair in a "bag", has shown some promise in bench-scale experiments (Schoeman & van Staden 1991). It is, however, harder to clean and maintain, as compared to the "un-sealed" E D process described above (Schoeman & van Staden 1991). Similarly, continuous deionization, which includes ion exchange resins in the clean water compartments of an E D stack, has been shown to produce very high quality effluent (Parekh 1991, Ganzi et. al. 1992). It also appears to be rather complex and potentially difficult to operate, as well as expensive to build (Ganzi et. al. 1992). Given the drawbacks inherent in both systems, neither sealed-cell E D , nor continuous deionization, appears to be a better option than the simpler, unaltered E D stack. One variation on the basic E D configuration which has significant benefits is electtodialysis reversal (EDR) (Applegate 1984, Schoeman 1985, Solt & Foster 1987, A W W A 1989). E D R is almost identical to E D . The only alteration has been the installation of mansformable cathodes and anodes. Rather than having the electrical current always travel in the same direction through the stacked filters (as it does in ED) , E D R uses an alternating current. The relative position of the anode and cathode are then dependent on the direction of electton flow (Figs. 3.3a & b). A s the locations of anode and cathode change, so too does the direction of ttavel for ions in solution. Cations and anions previously moving one way are now traveling in the opposite directions (Figs. 3.3a & b). Similarly, the compartments previously producing clean water now contain more contaminated water. The great advantage of this system is that it is "self-cleaning" (Applegate 1984, Schoeman 1985, Solt & Foster 1987, A W W A 1989). While operating under a given current, ions concentrate in certain areas of the E D or E D R filters, or stacks as they are more commonly known (Figs. 3.2 & 3.3a). Certain mineral salts, such as calcium carbonate (CaC03) or calcium sulfate (CaS04) have limited solubilities in water (Kotz & Purcell 1987). If those solubilities are exceeded, then salts w i l l start to precipitate. For example, if, as calcium and carbonate accumulate in the "contaminated" waters in the E D or E D R 20 stack, their combined ionic concentration is greater than the CaC03 solubility limit, then CaC03 wi l l begin to precipitate out of solution and onto the surrounding membranes. Precipitation wi l l continue until the combined abundance of calcium and carbonate ions is equivalent to the CaC03 solubility limit of water. When the direction of electricity changes in E D R , ions accumulate in different parts of the stack (Fig. 3.3b). As the previously contaminated compartment are drained of their ionic constituents, the concentrations of calcium and carbonate drop below the CaCC>3 solubility limit. Any precipitated CaCC>3 then re-dissolves, leaving an essentially clean membrane. Precipitates formed in a noimal E D stack have to be removed with acid or some other cleaning agent (Alsakari et. al. 1977, Schoeman 1985, Hughes et. al. 1992). Current reversal allows E D R to do this automatically and internally. O f the 4 available ion-selective technologies, E D and E D R are the most promising. E D R does appeal- to have certain inherent advantages over the simpler E D alternative. A more detailed comparison of the two systems has, however, yet to be discussed. 3.3.2 Water permeable membranes Unlike ion selective processes, water filtering systems are essentially sieves which capture and remove contaminants carried in the water as it passes through the membrane. Exactly which elements are removed is dependent upon filter pore size. As water slips through the pores, any particles or molecules larger than these spaces wi l l be trapped above the membrane. Filters with smaller pores can, therefore, filter out a broader range of substances. Tiny holed membranes do have certain restrictions. Water flow rates drop significantly as pores sizes shrink; it can reach a point where water has to forcibly pumped through the filter (Kalinske et. al. 1979, Applegate 1984, A W W A 1989, Cartwright 1991). Tighter membranes also have a higher probability of becoming clogged, as larger elements in the feedwater block pore spaces, or even cover up entire portions of the membrane wall (Applegate 1984, Parekh 1991). Although filters with tiny pores can strip a broader range of contaminants from a feed stream, using the tightest membrane is not always the best choice given the slower permeation rates and 21 higher clogging potentials associated with these filters. The success of a filtering system at the F N G P is, however, likely to depend on its ability to ek'minate the smaller molecular contaminants found within the plant's wastewater. Using a very tight membrane would, in this case, be unavoidable. There are several types of membranes designed for molecular sieving: ulttafilters (Applegate 1984, Jordain 1987, A W W A 1989, Ericsson & Hallmans 1994a), nanofilters (Rohe et. al. 1990, Kopp et. al. 1993, Wiesner et. al. 1994, Turner & Kadubandi 1994, Jacangelo et. al. 1995) and reverse osmosis filtration (Kalinske et. al. 1979, Applegate 1984, A W W A 1989, Parekh 1991, Mor in 1994). Ulttafilttation is the least effective of the three options; it can only remove substances measuring more than 0.005 um in diameter (Fig. 3.4). While bacteria, viruses and most suspended particles fall within these specifications (Applegate 1984, Jordain 1987, A W W A 1989, Ericsson & Hallmans 1994a), calcium, sulfate and other ionic elements w i l l pass unhindered through ultrafiltration membranes (Applegate 1984, A W W A 1989, Ericsson & Hallmans 1994a). Ultrafilters are restricted to relatively large particle removal. Nanofilters are slighdy tighter membranes. They can screen out ions as small as 0.0009 (im (Fig. 3.4). This includes many divalent species, such as calcium, sulfate, phosphate and magnesium (Cluff 1992, Kopp et. al. 1993, Fu et. al. 1994, Ericsson & Hallmans 1994b, Jacangelo et. al. 1995). Depending on their configuration, some monovalent ions, like sodium and chloride, can also be snipped out of solution using nanofiltration (Taylor et. al. 1989, Cluff 1992, Fu et. al. 1994). Nanofilters are not, however, very efficient at removing these singlely-charged elements (i.e. divalent removal rates can = > 95 %, monovalents rates are only around 35 % - Conlon & McCle l l an 1989, Taylor et. al. 1989, Cluff 1992, Comb 1994, Fu et. al. 1994). While able to eliminate a broader range of contaminants than ultrafilmation systems, nanofilters are generally only effective at removing the larger multi-valent ions from a feedwater su-eam. Reverse osmosis (RO) is the tightest membrane filter available. It can contain pores as small as 0.0001 | i m (Fig. 3.4). A s a result, it can efficiently strip monovalent ions (Hrubec et. al. 1979, 22 Osantowski & Geinopolos 1979, Kosarek 1979, Mor in 1994, Comb 1994, Page 1995) and even uncharged atoms (Kalinske et. al. 1979, Kosarek 1979, Applegate 1984, Eisenberg & Middlebrooks 1986, A W W A 1989, Wethern et. al. 1991) out of water. Of the three molecular sieves, R O is the most effective one at removing a wide range of contaminants. It therefore seems to be the best of the water permeable membrane filters. 3.3.3 Reverse osmosis vs. electrodialysis Within then- respective groups, E D / E D R and R O are the most promising of the available filtering technologies. Each method has inherent advantages and limitation. Key factors include their respective water recovery ratios, cleaning ability and robustness, as well as the technical expertise required to operate each system. Water recovery ratios R O : Unlike ordinary paper filters where water flows perpendicular to the membrane surface, R O feedwater travels parallel to the filter (Fig. 3.5). B y pressurizing the feed stream and limiting the exiting water flow, some water is forced through the R O membrane. The contaminants left on top of the filter are carried out of the unit in the remaining water. Therefore, two separate stream are produced by a R O membrane: a clean water, or permeate flow and a dirty water, or concentrate stream (Fig. 3.5). Permeate production is generally limited by 2 natural phenomena: osmotic pressure and particle diffusion (Applegate 1984,, Pohland 1987, Cartwright 1991). Unless acted upon by an outside force, water moves from areas of low solute concentration to zones of higher molecular abundance (Applegate 1984, Pohland 1987, Kotz & Purcell 1987, A W W A 1989). In R O , the reverse flow pattern is desired. High quality water is obtained by pushing liquid from the contaminated feed stream through to the relatively pure permeate side of the filter assembly (Pohland 1987, A W W A 1989, Parekh 1991). Feedwater pressure's must be greater than the osmotic pressure drawing clean water back across the membrane for there to be any permeate production (Applegate 1984, Pohland 1987, A W W A 1989, Parekh 1991). 23 A s water moves across a R O membrane, contaminant concentrations in the waste stream increase. The more concenttated the waste becomes, the greater the osmotic force pulling permeate back through the filter. Consequently, larger pressures are needed to ensure that the net flow of water is from concentrate to permeate. Eventually, as concentrate volumes get smaller and smaller, the pressure needed to drive the system wi l l exceed filter design, and the membrane wi l l burst. Water recovery rates in R O are therefore limited by the increasing osmotic pressure associated with higher permeate flows. Just as water naturally navels up the concentration gradient - from low concentrations to high ones, molecules diffuse down it - from areas of high concentration to those of low molecular abundance (Applegate 1984, Pohland 1987, Kotz & Purcell 1987, Cartwright 1991). Travel rates are determined by the magnitude of the concenu-ation gradient (Applegate 1984, Pohland 1987, Cartwright 1991). The larger the difference between the two zones, the greater the flow of molecules from one area to the other. So, as the concentrate stream in a R O filter gets more concentrated with higher permeate recovery rates, the gradient gets steeper. The flow of salts and other undesirable elements across the membrane subsequently increases and permeate quality decreases (Applegate 1984, Pohland 1987, Cartwright 1991). Due to the increases in salt passage and required feedwater pressures resulting from higher permeate production rates, individual R O units are typically resteicted to recovering 50 % of the incoming wastewater flow (Applegate 1984, Parekh 1991) To increase overall wastewater recovery rates, R O vessels can be linked in series. The concenttate produced in the first is directed into the second and so on until the desired output flow is obtained (Applegate 1984, Parekh 1991). Total recoveries are, however, limited by feedwater chemistry. Certain mineral salts are relatively insoluble in water (e.g. CaC03) (Kotz & Purcell 1987). A s a result, when ionic concentrations (e.g. C a 2 + and CO32") exceed solubility limits, these salts wi l l begin to precipitate out of solution. This is relevant to R O when one considers that any feedwater 24 entering an R O unit contains a given volume of water and a given mass of solute. The produced permeate wi l l be mainly water with few contaminants (if recovery rates < 50 %). The concentrate wi l l , on the other hand, consist of almost all of the influent contaminant mass dissolved in the remaining volume of water. Ionic concentrations in the R O waste stream are, therefore, higher than in the feed stream. If, at these "new" levels, the solubility of the sparingly soluble salts has been exceeded, then precipitation wi l l occur. The amount of water that can be withdrawn prior to precipitation is dependent on feedwater quality. If a wastewater is initially already close to the solubility limits, then very little water can be recovered before solids start to form. Alternatively, a good deal of water could be reclaimed from a waste sueam with very low scaling potential. Once precipitation has started to occur, membrane efficiency wi l l decrease rapidly, as portion of the membrane become coated with salt (Kosarek 1979, Pohland 1987, A W W A 1989, Huang & Koseoglu 1993, Noshita 1994). Although some solids can be removed with adequate cleaning (Eisenberg & Middlebrooks 1986, Pohland 1987), most filters wi l l need to be replaced i f salt precipitation has been extensive (Eisenberg & Middlebrooks 1986, Pohland 1987). R O water recovery rates are limited by osmotic pressure and molecular diffusion to around 50% per R O vessel. Greater recoveries can be achieved by running two or more units in series. Influent chemical characteristics wi l l , however, resuict the success of multi-stage R O fi l iat ion. Permeate can only continue to be produced i f the concentiation of the sparingly soluble salts is low. Once solubility limits have been exceeded, system performance wi l l fall, and costly repairs may be required. E D / E D R : For ion-selective processes, such as E D and E D R , product water volumes are independent of feedwater quality. They are, instead, determined solely by the configuration of an E D or E D R stack. A s indicated earlier, an E D or E D R unit consists of alternating cationic and anionic membranes grouped between a cathode and an anode, with water flowing through the spaces between the membranes (Figs. 3.2 & 3.3a). When electricity is added to the system, ions wi l l move out of certain compartments into the others (Figs. 8 & 9a). Clean water is -produced in 25 areas drained of their ionic elements, while the waters in neighbouring spaces become increasingly contaminated. The ratio of clean to dirty water compartments is always x : x-1, where "x" is equal to the number of spaces in the stack producing clean water (e.g. Fig. 3.2). Water recovery ratios for individual E D and E D R units are, therefore, between 50 and 60 % of the incoming flow (i.e. recovery rate = number of clean spaces / total spaces = x / (x + x-1) = x / (2x - 1)). To increase overall wastewater recoveries, concentrate can be reprocessed either by recycling it back through the same stack or tteating it in one or more downstream units (Applegate 1984, Schoeman 1985, Solt & Foster 1987). Cleaning efficiency R O : R O membranes contain extremely small pores. As a result, they are able to screen ions and other atomic particles from a liquid. R O filters have been found to have the following mean removal efficiencies: 94 % for total dissolved solids (TDS) (Light et. al. 1984, Pohland 1987, Marquardt et. al. 1987, Shah et. al. 1993, Noshita 1994, Abdula'aly & Chammem 1994), 96 % - divalent ions (Hrubec et. al. 1979, Kosarek 1979, Light et. al. 1984, Pohland 1987, Marquardt et. al. 1987, Shah et. al. 1993, Abdula'aly & Chammem 1994, Noshita 1994), 94 % - monovalents (Hrubec et. al. 1979, Kosarek 1979, Light et. al. 1984, Pohland 1987, Marquardt et. al. 1987, Shah et. al. 1993, Abdula'aly & Chammem 1994, Noshita 1994), and 82 % for total organic carbon (TOC) (Kosarek 1979, Marquardt et. al. 1987, Chin & Ong 1991). E D / E D R : E D and E D R systems, on the other hand, have much lower removal efficiencies. The product water from a given unit typically contains 53 % of the TDS (Alsakari et. al. 1977, Kawanishi et. al. 1994, Kawahara 1994), as well as between 40 to 45 % of the mono- & divalent ions (Alsakari et. al. 1977, Hughes et. al. 1992, Kawanishi et. al. 1994, Kawahara 1994), found in the feedwater. Furthermore, these systems can only act on charged particles (Applegate 1984, Schoeman 1985, Solt & Foster 1987, A W W A 1989, Huang & Koseoglu 1993). The abundance of silica, natural organics and other inert materials in both product and concentrate streams wi l l be identical and unchanged from feedwater concentrations. 26 Ionic diffusion is probably a key factor which resnicts the cleaning ability of E D / E D R . A s ions accumulate in the concentrate compartments, concentration gradients across the separating membranes would increase. This, in turn, should promote a greater flux of charged particles back into the product water. Given the average removal rates described in the literature (described above), the optimum balance between active ion displacement and passive diffusion appeal's to occur when product water concentrations are around 50 % of those of the feedwater. Feedwater quality wi l l influence how close to this apparent 50 % maximum E D / E D R processes can operate. The ability to concentrate ions within the dirty water spaces in an E D / E D R stack wi l l be bound by the solubility limits of sparingly soluble salts (Schoeman 1985, A W W A 1989, Huang & Koseoglu 1993). If a feedwater is rich in (say) carbonate and calcium, then few calcium and carbonate ions can be transferred into the contaminant compartments before calcium carbonate begins to precipitate onto the surrounding membranes. Given the ability of E D R units to periodically shed precipitated solids (see "Ion Selective Separation"), the performance of these systems w i l l be less affected by salt scaling. They should, therefore, be able to operate closer to the 50 % maximal removal rates. Just as overall R O water recovery ratios are restricted by feedwater scaling potential, so too is the cleaning ability of individual E D and, to a less extent, E D R stacks. Product water quality from one E D / E D R unit can always be improved by putting it through other downstream stacks (e.g. Alsakari et. al. 1977, Hughes et. al. 1992, Kawahara 1994). There are, as one might expect, limits to this process. Finished water volumes wi l l be reduced by 40 to 50 % per E D / E D R unit (see "Water Recovery Ratios"). Recycling the resulting wastewater would minimize these water losses, but the larger feedwater flows (i.e. original water + recycled concentrate) would necessitate a larger E D / E D R system. More importantly, however, overall cleaning efficiencies are in themselves restricted by product water purity (Applegate 1984, Solt & Foster 1987). 27 The driving force in this process is electricity. Water by itself is a relatively poor conductor of elecuicity. As a result, as ion concentrations in product water compartments decrease, the electtical resistance of these waters increases. More energy needs to be added to the system to maintain a current through the entire stack. Eventually, it becomes impossible to import enough electricity into the process to promote ionic displacement from product to concentrate waters. Finished water quality can no longer be improved, regardless of how many units it travels through (Applegate 1984, Solt & Foster 1987). E D and E D R systems can only influence charged particles. A single E D or E D R stack can remove approximately 50 % of the ionic load of the feedwater stream. Although cleaning efficiencies appear to be limited by ionic diffusion, an abundance of sparingly soluble salts in the feedwater can further reduce the effectiveness of a E D or E D R system. Finished water quality can be improved by running it through additional E D / E D R units. The design of such a system would, however, have to balance cleaner water against the costs of obtaining & maintaining the desired product water quality & quantity. Optimum TDS R O : Reverse osmosis units tend to most effective when feedwater TDS concenttations are between 2 000 and 3 000 mg/L (Kalinske et. al. 1979, Mor in 1994). E D / E D R : Both elecfrodialysis and elecfrodialysis reversal are generally most effective when dealing with an inlet TDS of less than 2 600 mg/L (Solt & Foster 1987, Cluff 1992, Kawahara 1994). Membrane fouling R O : R O filters can be fouled by a number of substances. Some of these elements w i l l affect any R O system, while others are membrane specific. The former category includes suspended and colloidal solids (Larson & Argo 1976, Kalinske et. al. 1979, Kosarek 1979, Pohland 1987, A W W A 1989, Suemoto et. al. 1994), silicates (Marquardt et. al. 1987, Kawanishi et. al. 1994, 28 Noshita 1994, Abdula'aly & Chammem 1994), salt scaling (Kalinske et. al. 1979, Kosarek 1979, Pohland 1987, A W W A 1989, Huang & Koseoglu 1993, Comb 1994, Noshita 1994), and microbes (Pohland 1987, A W W A 1989, Chin & Ong 1991, Noshita 1994, Abdula'aly & Chammem 1994, Suemoto et. al. 1994). "Extreme" p H conditions (Applegate 1984, Eisenberg & Middlebrooks 1986, A W W A 1989) and various oxidizing agents, such as oxygen & chlorine (Applegate 1984, Eisenberg & Middlebrooks 1986, Pohland 1987, A W W A 1989), are examples of the latter group. To protect R O equipment, these contaminants are removed from the feed stream prior to its filtration. Pretreatment trains can include multi-media filters (Hrubec et. al. 1979, Osantowski & Geinopolos 1979, Kaakinen & Moody 1984, Wethern et. al. 1991, Pankratz & Johanson 1992, Shah et. al. 1993), ulti-afiltration (Kaakinen & Moody 1984, Wethern et. al. 1991), activated carbon columns (Osantowski & Geinopolos 1979, Kaakinen & Moody 1984, Pohland 1987, Marquardt et. al. 1987, Wethern et. al. 1991), and chlorination (Larson & Argo 1976, Kaakinen & Moody 1984, Suemoto et. al. 1994) and/or dechlorination (Pohland 1987, A W W A 1989) stations all depending on the extent of feedwater contamination, as well as which elements are of concern. They also tend to be more extensive than systems used for E D and E D R protection, since R O filters, on the whole, are generally more sensitive to fouling than either E D or E D R ( A W W A 1989). E D / E D R : Similar contaminating agents affect E D and E D R membranes, including suspended and colloidal solids (Applegate 1984, Schoeman 1985, Solt & Foster 1987, Huang & Koseoglu 1993), oxidizers (Applegate 1984, Schoeman 1985), and microbes (Applegate 1984, Huang & Koseoglu 1993). Silicates, on the other hand, pose no threat to E D or E D R (Kawahara 1994), but organics can (Kalinske et. al. 1979, Applegate 1984, Schoeman 1985, Solt & Foster 1987, Huang & Koseoglu 1993). E D systems can also be detrimentally affected by salt scaling (Schoeman 1985, A W W A 1989, Huang & Koseoglu 1993). This is of less concern for E D R stacks, due to the self-cleaning mechanisms inherent in the process (see "Ion Selective Separation"). 29 Pretreatment trains for E D and E D R contain similar elements as R O units; they are, however, generally simpler than R O systems, due to the greater robustness of E D and especially E D R membranes ( A W W A 1989). Technical operation & maintenance R O : Reverse osmosis is a relatively straight forward process. Pretreated feedwater flows into a R O vessel, and exits either as concentrate or permeate (Fig. 3.5). The whole process is conuolled by flow meters, pumps and valves (e.g. Applegate 1984, Pohland 1987, Parekh 1991). Though regular chemical cleaning wi l l help to maintain optimal filter performance (Applegate 1984, Pohland 1987), R O membranes wi l l eventually need to be replaced. They have an average life span of about 5 years (Pohland 1987). Inadequate pretteatment, highly contaminated feedwaters or harsh operating conditions wi l l significantly reduce filter life (Applegate 1984, Light et. al. 1984, Pohland 1987). In any case, since R O membranes exist as individual units (e.g. Applegate 1984, Eisenberg & Middlebrooks 1986, Pohland 1987, Parekh 1991), it is relatively easy to isolate and replace a faulty or spent filter. E D / E D R : B y their very configuration, E D and E D R units are complex and potentially hard to maintain. A n E D / E D R stack contains between 100 and 600 membrane pairs sandwiched between a cathode and an anode (Applegate 1984, Solt & Foster 1987). Bounded by each pair is a clean and dirty water compartment (Fig. 3.2). Water is carried to and from each opening in separate tubes. Fresh water is also continually traveling over the cathode and anode to keep them free of contaminants (Applegate 1984, Solt & Foster 1987). This results in an extensive array of pipes and valves, in addition to the equipment conttolling the flow of electricity to and from the stack. E D R has the additional complications associated with periodic current changes. When the flow of electricity changes direction, product water compartments become filled with concenmite, and vice versa (Figs. 3.3a & b). The stack has to be purged before product water can be collected from its new locations to prevent contamination with any remaining concenttate (Applegate 1984). A s a 30 result, E D R units have even more complex valving systems than E D stacks (Applegate 1984, Schoeman 1985). Whichever process is used, E D or E D R , the operators wi l l have to be familiar with both water flow and elecnical instrumentation, and they must be able to identify potentially problematic situations before they disrupt the E D or E D R cleaning process. A s previously mentioned, there are between 100 and 600 cell pairs in a E D / E D R unit, and water ttavels to and from each membrane set in a separate tube. There are, as a result, hundreds of tiny pipes running into and out of a single stack! If one of these tubes were to become blocked, locating the problem could take some time. Similarly, i f a membrane should fail or wear out, a good portion of the entire stack would have to be disassembled to find and replace the spent filter (Hughes et. al. 1992). Any time a stack is taken apart, be it for manual cleaning or membrane change, there is generally a high probability of membrane damage (Applegate 1984, Hughes et. al. 1992). Clearly, maintaining a E D or E D R system can be both time and labour intensive. Where as R O technology offers simplicity and ease of operation, E D and E D R are complex, potentially time consuming reclamation processes. Technical personnel would require greater training to operate and maintain such systems; maintenance cost are also likely to be higher than those associated with R O . The better system R O is slightly more sensitive to fouling than either E D or E D R , and, as a result, generally requires more extensive pretteatment systems (Table 3.1). Even though average water recovery rates per operating unit are almost equivalent for E D , E D R and R O (Table 3.1), overall product water volumes also tend to be greater for E D and E D R . Product water quality is, on the other hand, likely to be better with R O , due to more efficient removal of a broader range of contaminants (Table 3.1). The best feature of reverse osmosis is its simplicity and operational ease, especially when compared to the more complex E D and E D R technologies (Table 3.1). In face of all of the above criteria, reverse osmosis appears to be the most effective membrane f i l ia t ion system. 31 3.3.4 RO membranes selection R O membranes are derived from either cellulose acetate (Applegate 1984, Eisenberg & Middlebrooks 1986, Pohland 1987, A W W A 1989) or poly-organic compounds, such as polyamide (Applegate 1984, Eisenberg & Middlebrooks 1986, Pohland 1987, A W W A 1989). Cellulose-based membranes (CAs) are generally cheaper than polyamides (PAs) ( A W W A 1989). They are also more resistant to oxidizing agents, such as chlorine and dissolved oxygen, than PAs (Applegate 1984, Eisenberg & Middlebrooks 1986, Pohland 1987, A W W A 1989). On the other hand, PAs can operate under broader temperature and p H conditions, (Eisenberg & Middlebrooks 1986, A W W A 1989 for the former; Applegate 1984, Eisenberg & Middlebrooks 1986, A W W A 1989, Abdula'aly & Chammem 1994 for the latter). They are also resistant to biological degradation (Shields 1979, Applegate 1984, Pohland 1987), unlike C A s (Applegate 1984, Eisenberg & Middlebrooks 1986, A W W A 1989), and PAs require lower water pressures than C A s to produce a given permeate flow ( A W W A 1989). As both membrane types generally have the same filtering abilities, either one could be used in any treatment system; the R O pretreatment ttain would simply have to be designed to produce the required feedwater characteristics (e.g. proper p H , temperature, dissolved oxygen and chlorine levels...). R O filters, regardless of their individual make-up, come in one of 4 different configuration: tubular (Eisenberg & Middlebrooks 1986, Pohland 1987, A W W A 1989, Parekh 1991), plate-and- frame (Pohland 1987, Eisenberg & Middlebrooks 1986, A W W A 1989, Parekh 1991), hollow- fibre (Eisenberg & Middlebrooks 1986, Pohland 1987, A W W A 1989, Parekh 1991), and spiral wound (Eisenberg & Middlebrooks 1986, Pohland 1987, A W W A 1989, Parekh 1991, Mor in 1994). Plate-and-frame, as well as tubular designs, while effective, have limited applications. Their relatively small membrane surface area to unit volume ratios (165 & 335 m 2 / m 3 , respectively - Pohland 1987) makes treating anything by very small feedwater flows extremely expensive (Pohland 1987, Parekh 1991). 32 Both spiral wound and hollow-fibre membranes have much larger area to volume ratios (1 000 & 16 500 m 2 / m 3 , respectively - Pohland 1987). The use of hollow fibre systems has been restricted in the past by their relative sensitivity to fouling (Applegate 1984, Pohland 1987), and their need for higher feedwater pressures (Morin 1994). As a result, the operating costs associated with hollow fibres are greater than those for spiral would designs (Morin 1994). The dominance of spiral would membranes is also due in part to the ease with which recent advances in membrane technology have been incorporated into these designs as compared to hollow fibre configurations ( A W W A 1989). Thus, although membrane type is a somewhat arbitrary choice based on feedwater characteristics, treatment system generally always use spiral-wound R O filters, because of the relative robustness and low cost of this configuration. 3.4 Brine Disposal Regardless of whether distillation, ion-exchange or membrane filtration is used, each system wi l l produce a final wastewater requiring further treatment; these waters could be either regeneration fluids from the ion-exchanges, very concenttated blowdown flows from the distillation vessels or R O membrane concenttates. As the goal of the Z E D project is to completely eliminate the need for a wastewater discharge from the F N G P , none of the previously discussed technologies is, on its own, sufficient to fulfill this objective. Power plants and other zero-effluent facilities described in the literature (e.g. Brew & Blackwell 1991, Pankratz & Johanson 1992, Bowlin & Ludlum 1992, Pierce & Sbei 1993, Sttauss 1994) which have similar water demands as the F N G P (i.e. make-up water to replace boiler and other process losses) incorporate one of two systems into their wastewater treatment trains. Concentrated liquid wastes are either disposed of in evaporation ponds (Bowlin & Ludlum 1992, Pierce & Sbei 1993), or they are solidified prior to discharge and landfilled (Brew & Blackwel l 1991, Pankratz & Johanson 1992, Bowl in & Ludlum 1992). Evaporation ponds are rather self-explanatory. Wastewater drains into the holding ponds and evaporates. The remaining solids collect in the basins, which are eventually capped with earth. 33 Wastewater solidification, on the other hand, tends to be best carried out in two steps. Concentrate volumes are first reduced through forced evaporation using a brine concenttator (B/C) (Brew & Blackwell 1991, Bowl in & Ludlum 1992, Pankratz & Johanson 1992). This robust piece equipment is specifically designed to handle veiy contaminated liquids. It is not affected by the precipitation of salts and other solids, typically formed during wastewater evaporation. Rather than coating the inner workings of the B / C , these substances precipitate onto seed elements added to the feed stream as it enters the unit (Pankratz & Johanson 1992, Bowl in & Ludlum 1992). B/Cs can recover up to 90 % of the incoming wastewater (Brew & Blackwell 1991, Sttauss 1994), and product water quality is very high (< 10 mg/L TDS - Bowlin & Ludlum 1992, Pankratz & Johanson 1992). The remaining 10 % exits the B / C and travels to the second part of the solidification process. Brine concentrator wastes can go to either a spray dryer (Brew & Blackwell 1991, Bowl in & Ludlum 1992), or a crystallizer (Bowlin & Ludlum 1992, Pankratz & Johanson 1992). Wastewater entering a spray drying is atomized into tiny droplets, which then fall through a hot air chamber. Water evaporates, and the remaining solids fall into a collection basin at the bottom of the unit. The produced material tends to be very fine and powdery, because it forms from tiny water drops. It is completely dry, and can be directly landfilled (Brew & Blackwell 1991, Bowlin & Ludlum 1992). Crystallizers work somewhat differently. Hot, pressurized wastewater is injected into a hollow-bodied vessel (Bowlin & Ludlum 1992, Pankratz & Johanson 1992). A s the pressure in the tank is less than that of the feedwater, flash evaporation occurs. Not all of the feed stream vapourizes at once; some of it remains as a liquid. This water falls to the bottom of the vessel, along with any newly-formed solids. Some of this solution is recycled back through the process, while the remaining portion is drained from the system. This bleed stream is generally further dewatered with a filter press (Bowlin & Ludlum 1992, Pankratz & Johanson 1992). The resulting solid filter cake can then be landfilled. 34 About 75 % of the feedwater flowing to a crystallizer wi l l be turned to steam, which can be recovered and reused (Pankratz & Johanson 1992, Bowlin & Ludlum 1992). Spray dryers are not designed for steam recovery; any and all vapourized water is lost to the atmosphere (Brew & Blackwel l 1991, Bowl in & Ludlum 1992). These units are, on the other hand, a final solution. Incoming wastewater is completely transformed to a dry solid. There is no need for additional dewatering equipment, as is the case with crystallizers. Capital and operating costs are, therefore, likely to be lower for Z E D operations using spray dryers instead of crystallizers. The fine, powdery nature of the solids produced by a spray dryer can, however, make them difficult to handle (Brew & Blackwell 1991). In summary, the small volumes of wastewater draining from distillation, ion-exchange or membrane filtration processes can be disposed of either in evaporation ponds or by more energy intensive forced evaporation systems. Such a system is likely to include a brine concenn-ator and a crystallizer or spray dryer. Regardless of its configuration, any brine disposal technology wi l l produce two outflows: relatively pure water, which either escapes to the atmosphere or is collected and reused, and a solid waste, either in the form of precipitates in an evaporation pond, fine powder from a spray dryer or a filter cake from a crystallizer/filter press assembly. 3.5 Conclusion Current literature clearly indicates that the F N G P can become a Z E D facility. The required technology exists, and other facilities with similar water demands as the F N G P already operate under a Z E D framework. A wastewater recycling program at the F N G P is likely to use either distillation, ion-exchange or R O as the main treatment process. Remaining concentrates wi l l be directed into either an evaporation pond or a brine concentrator - spray dryer or crystallizer assembly. Wastewater currendy leaving the plant wi l l be reduced to a solid waste. 35 Table 3.1: A comparison of the inherent advantages and disadvantages of reverse osmosis (RO), electrodialysis (ED) and eiecnodialysis reversal (EDR). Parameter RO ED EDR Water recovery rate / vessel 50 % max. 50 - 60 % Removal rates: total dissolved solids (TDS) 94 % 53 % monovalent ions 9 4 % 5 5 % divalent ions 96 % 60 % total organic carbon 82 % Can it remove non-ionic particles? Yes N o Optimal TDS - mg/L 2 000 - 3 000 < 2 600 Fouling elements: Salts Yes Yes Microbes Yes Yes Silica Yes N o Organics N o Yes Solids Yes Yes Relative pretreatment needs High Moderate Operation & maintenance Simple Complex 50 - 60 % 53 % 55 % 6 0 % N o < 2 600 N o Yes N o Yes Yes L o w Highly complex 36 100000 10000 1000 TDS (mg/L) 1 00 1 o- Membranes Distillation Ion-exchange Desalination Technology Figure 3.1: Typical operating total dissolved solid (TDS) concentrations for different desalination technologies. - adapted from A W W A 1989 37 T3 O3 8 £ 03 oo c c P H O •5 03 u 03 <u c o c < -8 o 03 u D 03 oo 03 + + < + < -A 6 < + < -A *1 a % O a < t-c D 03 oo U . S " i I I 13 U -*-» c I I is <U 03 O > G <0 < g c c • i <5 <6 1 E > .5 • r t •<-> O ° oo 5 / 2 < u OO oo <U O O S-l OH 00 13 •-3 o is o JU 13 <u J3 -<—» <H-H o c o •a oo 3 3 j C < U 3' SJD OO 0 \ -4—t 03 00 <D *—* QH OH < s O -a o3 38 Rinse water 4 Product water Anode Rinse water 4 Direction of electron flow | t. t • t t •> Concentrate Cathode Wastewater Rinse water Rinse water Figure 3.3a: Flows through an EDR stack when electricity travels from right to left. Rinse water A Rinse water Concentrate Cathode Direction of electron flow Product water t t t f t t ( Anode Wastewater Rinse water Rinse water Figure 3.3b: Flows through an EDR stack when electricity travels from left to right. - adapted from Applegate 1984 39 40 41 4.0 METHODOLOGY 4.1 Analysis of the Existing Water Distribution Network 4.1.1 Flow data Data collection: Water flow data used herein are a collection of metered readings, derived values, and numbers provided by plant personnel. Metered measurements originated from a number of sources. Some of the information was available in operational reports and other hard copy documentation. Other readings were extracted from the facility's continual monitoring computer system. Only several months worth of data was renievable from the computer network. January 1995 was one of the few months where a complete set of measured values was available. A l l of the metered numbers used in this study were average flow rates recorded over those 31 days. Data analysis: Water balances were used in conjunction with flow diagrams to identify leak points in the FNGP ' s water distribution network. One set of balances was developed around the individual operating units within the plant (e.g. Powerhouse, E & F Process Trains and the Sulphur Plant). A second group followed each water loop through the entire facility (e.g. 450 and 45 psi steam systems). If the difference between total input and total output in a given balance was less the 10 %, the system was considered balanced. 4.1.2 Chemical data Data collection: Water samples were collected by plant personnel from a number of different locations in the water distribution network (Fig. 4.1). A I L and a 200 or 250 m L acid-washed polyethylene bottle were filled at each sampling station. Nitric acid was added to the smaller container to lower its p H to < 2 p H units; the acid was used as a preservative to stabilize metal concentrations within these samples (Greenberg et. al. 1992). No acid was added to the larger bottle, because this water was used to determine pH, alkalinity and a number of other "acid- 42 sensitive" parameters. Sampling generally occurred twice a week for three weeks in May 1995 1. A n additional set of samples was later collected in mid-July to evaluate developing trends in the data. A t the completion of each round of sampling, full bottles were placed into a cooler with frozen ice packs, sent to the University of British Columbia's Environmental Engineering Lab, and, upon arrival, were stored at 4 °C until they could be analyzed. Upon removal from the refrigerator, the 1 L bottles were shaken and 80 rnL of water was withdrawn from each for a total solids determination. The remaining waters were then filtered through 0.45 Jim pore membranes and analyzed for acidity, conductivity, alkalinity, total carbon content (both organic and inorganic), and various inorganics (i.e. sulphate - SO4, phosphate - PO4, chloride - C l and silica - Si). Acidity and conductivity were measured with a Beckman 044 p H probe and a Fisher Scientific Accumet® conductivity meter, respectively. Alkalinity was tested by titration (Greenberg et. al. 1992). Inorganic concentrations were determined by a Lachat Quickchem Flow Injection Analyzer, while a Shimadzu TOC-500 (total organic carbon) analyzer was used to identify both inorganic and organic carbon content. Acidified waters from the smaller 200 / 250 m L containers were also filtered prior to examination. These waters were analyzed for calcium (Ca), magnesium (Mg), sodium (Na) and iron (Fe) using A A S (atomic absorption spectrophotometry) following methods described in Thermo Jan-el Ash (1986). A l l of the tested parameters were chosen based on their importance to boiler maintenance and operation (Jackson 1980, Robertson 1981, Schroeder 1991). A key part of the F N G P water network are the three boilers used to generate steam for the facility. They have the most stringent water quality requirements of all of the equipment in place at the plant (Shang Su, personal com.). 1 The time lapse between the collection of water flow and water chemistry data was due to the desire to fully analyze the flow data prior to water sampling. Developing a complete image of the plant's water distribution network before initiating the sampling program ensured that all of the pertinent water flows were sampled. 43 B y identifying the abundance of the selected contaminants in different parts of the plant, Z E D equipment can be designed to produce water clean enough to maintain current B F W quality, thereby ensuring a successful wastewater recycling program. Data analysis: Some waters contained contaminant concentrations below detection limits. These samples were subsequently assigned the detection limit value. This value replacement procedure pertained only to the inorganics and the metals; the detection hmits were 0.1 mg/L for C l , 1.0 mg/L - S 0 4 , 0.05 mg/L - P 0 4 , 0.1 mg/L - Si , 0.05 ppm - Ca, 0.10 mg/L - M g , 0.04 mg/L - Fe and 0.02 mg/L for sodium. Several individual observations were deemed non-representative and dropped from the data set, because they were either illogical (e.g. total carbon < organic carbon) or equal to ± 2 x the average value of the remaining readings. Two entire samples were also tossed out of the study, since more than 50 % of their defining parameters were found to be non-representative, as defined above. For example, discarded measurements included sodium and alkalinity readings from the M a y 24th treated water sample (Appendix C). The two completely omitted samples were the May 3rd reservoir and July 12th raw water samples (Appendix C). The remaining data set was used in conjunction with water flow information to form mass balances of the water network. These balances were used to determine i f all pertinent chemical and water flow paths had been accounted for, as well as to deteimine which of the plant's discharged waters could be directly reused, and which others would require treatment before being pumped back into the water system. 4.2 Select the Appropriate Recycling Technology for the FNGP Components for the FNGP's Z E D system were chosen based on their: • ability to perform effectively at the plant • relative capital and operating costs • ease of operation 44 associated safety risks 4.3 The Computer Simulator 4.3.1 Basic construction A computer simulator was constructed to determine the "best method" of transfonning the F N G P into a Z E D facility. It was built in a 2-step process. A l l of the data collected at the plant was first imported into Microsoft Excel® to form a static image of the water distribution network. Sources and sinks identified in previously assembled mass balances were included to this model 2 . Most of the inputted data were then replaced with numerical formulas. The values displayed in one part of the simulator were now either directly or indirectly linked to the rest of the system. With the interlinking equations in place, changing the value of a given cell resulted in the recalculation of the whole worksheet. The formulas themselves were derived from either assumption, information available in various F N G P training manuals (e.g. calcium concentrations in lime treater blowdown were calculated from data in the Water Treatment Manual), patterns in the collected data (e.g. chloride concentration in lime tteater blowdown were the same as the raw inlet water) or a combination thereof. Every equation and its derivation is listed in Appendix E . Key assumptions used in building the. simulator were: • A l l identified sources and sinks were assumed to stay constant over time, and they were incorporated into the simulator as a percent increase or decrease, respectively. • Regardless of influent characteristics, softened water leaving the ion-exchangers always had j calcium and magnesium concentrations equal to those now found in the tteated water used at the 2 A source or sink was defined as a difference of > 15 % between the total incoming and outgoing mass flux through a given system. The only source or sink that was not included in the simulator was a > 15 % discrepancy in iron levels across the polishing pond. This observation was dismissed as an error; when the metal samples were acidified just after collection, bound iron was probably released from algae present in these waters. 45 F N G P (i.e. 1.4 mg of Ca /L and 0.5 mg of M g / L - Appendix C) . Changes in feedwater hardness would only influence the rate at which the ion-exchangers needed to be regenerated, and not product water quality. • A l l treated water losses from the system, except for the boiler, sulphur plant and lime neater blowdowns, as well as the 8 psi steam and ion-exchanger regeneration flows, were constant over time. • Raw water chemistry was also constant over time, as were the p H readings of the boiler, sulphur plant and lime treater blowdowns and the flow of domestic filter backwash and pump sealant to the lime pond. These assumptions, combined with observable uends in the original data, were used to assemble formulas which transformed the static model into a predictive simulator. A l l of the worksheet cells were interlinked. A change in any patt of the water network now either directly or indirectly affected the rest of the system. 4.3.2 ZED components The different recycling technologies (e.g. R O , B / C and spray dryers) were themselves represented by equations. Contaminant loads in concentrate and product waters were derived from waste removal rates found in the literature. Maximal water recovery rates for R O , B / C and other Z E D vessels were also taken from published work. Together, contaminant load and exiting flow calculations served to define the products leaving any of the Z E D components. Building different Z E D treatment trains was simply a matter of linking the pertinent recycling units together. The assembled systems were then individually connected to the water network. A s each cell in each computer worksheet was influenced by all of the other cells, the model automatically re-adjusted itself to account for any changes induced by the different Z E D designs. 46 4.3.2 Parameter values Incorporated into the simulator are a number of variables which can be altered by a user. They include, for example, the volume of 8 psi steam lost through venting and the final waste disposal system. A l l told, there are between 16 and 44 variables open to manipulation, depending on the chosen Z E D configuration. During testing, the values of certain parameters, such as the number of R O stages incorporated into a treatment ttain and the presence or absence of a brine concentrator, were automatically determined by the nature of the simulation. If the selected Z E D design was a 1-stage R O with a B / C , then clearly only 1 R O stage was used and a B / C was included in the simulation. Each Z E D configuration therefore imposed certain restrictions on a user's freedom to further manipulate the simulator. Of the independent variables not affected by a given Z E D design, a few were kept constant throughout the evaluation process to maintain comparability between different scenarios. They included: • R O and B / C contaminant removal efficiencies • 8 psi steam losses, which were kept at zero • a continual flow of 171 m 3/day of condensed 8 psi steam to the hot lime treater • water temperatures of 35 °C within the R O filters • water p H values of 5.8 at the entrance of every R O filter stage • water recovery rates of 50 % on the first R O unit • B / C water recovery rates of 90 % The specific values were selected based on either current conditions at the plant (i.e. 171 m-Vday of 8 psi steam to the lime treater), opportunities for system optimization (i.e. closing the 8 psi steam vents), or information in the available literature (e.g. previous research indicates that membrane filters tend to work most effectively when feedwater temperature and p H are between 30 47 to 50 °C (Kalinske et. al. 1979, Applegate 1984, A W W A 1989) and 4 to 7 (Applegate 1984, A W W A 1989, Suemoto et. al. 1994), respectively). The remaining parameters were changed during each simulation to provide a realistic, yet optimal view of the water distribution network under a Z E D framework. For example, literature indicates that maximal wastewater recovery rates for R O filtration are 50 % per stage (Applegate 1984, Parekh 1991). Ideally, the F N R discharge could be filtered through a 2-stage R O , with each unit operating at 50 % recovery. The waste stream would then be reduced to 25 % of its original volume. Calcium, carbonate and sulfate concentrations in the composite wastewater are, however, high enough that at this level of tteatment the R O membranes would quickly become contaminated with precipitated calcium salts. The process, while appealing to be very effective in terms of waste reduction and water recovery, would be unrealistic, due to the high salt content of the wastewater. A balance was therefore maintained between calcium pretreatment and water recovery rates to maximize the rate of wastewater reclamation while ensuring filter integrity. The final configuration of every tested Z E D design was recorded, and the inputted parameter values are listed in Appendix F . 48  5.0 ANALYSIS OF THE EXISTING WATER DISTRIBUTION NETWORK 5.1 Results 5.1.1 Water balances A l l of the individual operating units were in balance (Table 5.1), as was each water loop (Table 5.2). The only exception was the effluent plant. Almost 1/3 of the wastewater collected at the effluent plant seemingly disappeared during treatment (Table 5.1). Plant personnel have indicated that this discrepancy may have resulted from faulty or inaccurate flow meters, as opposed to actual water losses (Bruce Kosugi, personal com.). The general balance of the water system seemed to indicate that all major flow paths had been identified and accounted for. Numerous steam leaks and/or water discharges were discovered in the water system. Obviously, the effluent plant was one area of potentially significant water loss, should the flow meters prove to be accurate. Other pathways by which water escapes from the plant are fisted in Table 5.3. While some of these flows were quite large (i.e. > 150 m3/day), others were relatively insignificant (i.e. < 5.0 m3/day) (Table 5.3). A l l in all, the water distribution network seems to have been properly detailed, and the presence of leaks and other drainage points within the plant's flow network may indicate that the existing system can be optimized. 5.1.2 Mass balances Mass balances were performed on 5 areas of the plant: the front-end softeners, the lime and polishing ponds, the sulphur plant and the boilers. There were large inequalities in each balance. The front-end softener (FES) and lime pond mass balances were perhaps the worst of the bunch. Significant amount of mass (i.e. > 15 % of the total incoming flux) were missing from the FES balance for all but 2 parameters (Table 5.4). Similarly, the lime pond appeared to be a source of calcium, chloride, magnesium and a number of other chemicals, while also acting as a carbon, iron and phosphate sink (Table 5.5). Generally fewer than half of the 16 monitored parameters were significantly skewed in the remaining three mass balances (Tables 5.6, 5.7 & 5.8). In any case, 50 the presence of so many large discrepancies calls into questions the quality of the collected chemical data. 5.2 Discussion 5.2.1 Data quality Water flow numbers: The representative value of the water flow data set may at first seem somewhat suspect considering that it contains a number of readings averaged over only 1 month of the year. The January 1995 averages were, however, generally within 10 % of mean flow volumes derived over longer periods of time (Table 5.9). Even when the difference between the 2 average values was greater that 10 %, it was rarely a significant difference (tstatistic > 1-96, p < 0.05) (Table 5.9). The January 1995 data should, therefore, be representative of general flow patterns at the plant. Although the January 1995 metered data may be representative of longer term trends, several of the flow meters from which these numbers originate may not in themselves be accurate. As previously mentioned, plant personnel have indicated that the observed water leak at the effluent plant may have been the result of faulty flow meters. Furthermore, according to the inlet and outlet flow meters on the front-end softening system, about 538 and 725 m3/day entered and exited the FESs, respectively (Table 5.9). At these flow rates, there would appear to be a major hole in the incoming raw water pipeline, as well as insufficient treated water make-up to replace all of the treated water now lost from the plant (Table 5.10). If one calculates the raw and treated water flow rates by a heat balance on the 8 psi steam loop (Appendix B), then the volumes of incoming raw water and outgoing treated water increase and the pipeline leak and treated water deficit disappear (Table 5.10). This discrepancy between the metered values and the calculated flows indicates that there may be, or at least have been, inaccurate flow meters at the plant, and that part of the collected data set may contain inaccurate numbers. If incorrect information was used to analyze the water distribution network, the resulting water and mass balances could be wrong. Individual flow paths could have been missed, and/or leak 51 points may have been overlooked or underestimated. Yet, considering that plant personnel have repeatedly examined the resulting water balances (hence the discovery of the apparently inaccurate flow meters on the FESs), it is unlikely that the flow data continue to contain any serious flaws. It is, therefore, reasonable to conclude that the plant's water distribution network has been adequately defined by the collected data to proceed with the Z E D project. Chemical data: The large number of inequalities found in the 5 mass balances performed on different areas of this facility seemed to indicate that plant waters were either mis-sampled and/or improperly analyzed, or that additional flow paths remained unaccounted for. With respect to the FES balance, it was concluded that given the amount of chloride and sodium missing from the balance (Table 5.4) the regeneration waters from the ion-exchangers were never correctly sampled. Information in the Water Treatment Manual also indicates that the description of the hot lime treater blowdown waters was probably incorrect The hot lime treater removes calcium, magnesium, silica and inorganic carbon from incoming raw water by causing these substances to precipitate. The resulting solids are then carried to the • lime ponds within this vessel's blowdown stream. As previously discussed, filtered non-acidified water was used for silica and alkalinity measurements. Any solidified silica and/or carbonate within the collected blowdown waters would not have been detected. Similarly, the low recorded concentrations of calcium and magnesium in these waters (Appendix C) suggests that not all of the solidified calcium and magnesium was available for observation in the acidified metal samples. As a result, the large discrepancies in the FES mass balance were likely due to incorrect sampling of the ion-exchangers' regeneration brine and underestimated contaminant concentrations in the hot lime blowdown sample, rather than unidentified outflows from the softening system. Using information from the Water Treatment Manual, it was possible to estimate what the ion- exchange and hot lime treater wastewaters should have looked like (Appendix D). Recalculating the mass balance with these altered outflows showed the front-end softening system to be in near 52 perfect balance; there were significant differences in only 4,-instead of 10, parameters (Table 5.11). Problems with the original characterization of the front-end softening system was also responsible a large number of the inequalities found across the lime pond. For example, the lime pond appeared to be a source of calcium, magnesium, sodium and chloride (Table 5.5), because the influx of these elements from the hot lime ffeater and ion-exchangers was underestimated. When the lime pond mass balance was reworked with the calculated FES outflows, these chemical surpluses disappeared (Table 5.12). Yet, rather than resulting in an even balance for all 4 elements, the lime pond turned from a source of calcium and magnesium to a sink for these 2 chemicals (Table 5.12). It also continued to be a sink for silica and inorganic carbon (Table 5.12). Considering that these contaminants are flushed from the hot lime treater as precipitates, these findings are, in retrospect, hardly surprising. The calcium, magnesium, silica and inorganic carbon flowing into the lime pond from the hot lime tieater were partof the suspended solids which settled out of solution within the lime pond, hence its appearance as a sink for these chemicals. B y the same logic, it is not unreasonable to assume that the iron, organic carbon and phosphates missing from the lime pond outflow also precipitated out of solution, either on their own or as part of larger settlable solids. The 3 remaining mass balances were unaffected by the problems with the ion-exchanger and hot lime treater samples. Discrepancies in these systems can, however, be attributed to other causes. Conditioning chemicals added to the boiler feedwater used in the both the boilers and the sulphur plant, while having very little effect on flow volumes, alter the chemical characteristics of this water (Nalco Chemical Program). They are, as a result, responsible for several of the inconsistencies observed across these 2 systems (Tables 5.6 & 5.7). Similarly, water samples taken from the polishing pond always contained algae. These organisms were likely the cause of the significant differences between total incoming and outgoing suspended solids, phosphate, dissolved organic carbon and iron (Table 5.8). For example, their mere presence would have 53 increased the level of suspended solids within these waters, and iron bound within the algae was also probably released into solution when the metal samples were acidified just after collection. The results from the initial mass balances suggested that there were major problems within the assembled chemical data set. Further investigation showed that several areas of the F N G P had indeed been mis-sampled. There was, however, information available at the plant which was used to more accurate characterize of these flows. Reworking the mass balances with these new estimates eliminated a large number of the originally observed inconsistencies. Some of the remaining problems were attributed to other previously overlooked factors, including the addition of conditioning chemicals to the boiler feedwater tanks and the presence of algae in the polishing pond. Since many of the discrepancies observed in the original mass balances can be explained or completely eliminated, the chemical data collected at the plant, including that contained in several operation manuals, provided sufficient information to indicate that all pertinent water flows had been identified and characterized, and that one could now proceed with the design of a Z E D system for the F N G P . 5.2.2 System optimization A s previously discussed in the inuoduction of this report, optimizing the plant's water distribution network wi l l not only reduce the demand for treated water make-up, which can lead to subsequent reductions in a Z E D system's final waste output, it wi l l also limit the size, complexity and cost of the required Z E D treatment train by limiting the volume of wastewater requiting purification prior to reuse. Increasing the efficiency of the existing water network can be achieved by closing off leaks in the system and by reusing relatively uncontaminated waste streams currently released from this facility. Water leaks: The F N G P already appears to have quite a tight distribution network, as only 2 leak points were uncovered while compiling the water balances. They consisted of steam escaping from the plant's steam tracing pipes and wastewater lost from the effluent plant during treatment (Tables 5.3 & 5.1, respectively). While sealing up holes in the steam tracing network wi l l 54 theoretically reduce the demand for treated water make-up, the actual benefits of such action may be somewhat inconsequential. The volume of escaping steam was estimated at 5 m 3/day (Table 5.3). This is less than 1 % of the total volume of treated water now produced by the FESs (Table 5.1). Clearly, altering the state of the steam tracing system wi l l have very little, i f any, affect on the rest of the water network and/or the success of a Z E D program at the plant. The leak at the effluent plant was somewhat larger than the one in the steam u -acing pipes. It was estimated at 50 m 3/day, almost 1/3 of the effluent plant's total mcoming water flow (Table 5.1). Despite its apparent size, the disappearance of wastewater from the effluent plant does not affect the tteated water system. The effluent plant mainly receives domestic sewage and dirty raw water. If more or less water were to escape from the effluent plant, treated water make-up demands would remain unaffected. Recovering the lost effluent plant wastewater is not, therefore, going to affect a Z E D system's waste output in the classic sense of increasing or decreasing waste production at the FESs. It wi l l , however, alter the size of the required Z E D treatment train and the volume of waste drained from this system, as indicated by tests with the computer simulator. When the leak was initially sealed, the volume of the F N R discharge jumped from 282 to 332 nvVday (Table 5.13). Similarly, the mass of solid waste leaving the Z E D system increased from 415 to 483 kg/day (Table 5.13). Although both the volume of wastewater going into the Z E D treatment train and the mass of solid waste leaving said system dropped when reclaimed wastewater was recycled back through the plant, they still remained at higher levels than when the leak at the effluent plant was left untouched (i.e. 285 vs. 240 m3/day and 294 vs. 233 kg/day, respectively - Table 5.13). The reason for the sustained increase in both measurements is the abundance of contaminants in the effluent plant outflow relative to the FNGP' s raw water inflow (e.g. T D S readings of 2850 vs. 400 mg/L, respectively - Appendix C) . When the leak at the effluent plant was sealed, all of the contaminants previously escaping through this "hole" were added to the water system, and, although the flow of raw water into the F N G P did decrease below "open leak" levels once wastewater recycling was initiated, this flow reduction was insufficient to 55 prevent anet increase in the flux of contaminants through the plant's water network. A s a result, the plant produced a larger waste flow containing more contaminant mass than when the leak was left untouched. Eliminating possible wastewater losses from the effluent plant w i l l not, however, outright abolish the opportunity to initiate a Z E D program at the F N G P . Operational water losses were found to be in excess of 600 m 3/day (Table 5.3). Effluent plant outflows were only 109 m 3/day (Table 5.1). Even i f all of the wastewater lost from the effluent plant were recovered, effluent plant outflow would still be far less than current operational losses (i.e. 160 m 3 /day vs. > 600 m 3 /day - Tables 5.1 & 5.3, respectively). The limits imposed by this project's first boundary condition have not been violated; the FNGP's domestic wastewater production rates are smaller than their operational water losses, and they would continue to remain so even i f all of the wastewater observed to be escaping from the effluent plant were recovered. A Z E D program can therefore be implemented at the F N G P without recycling any reclaimed wastewater through the domestic water system. It is was initially suggested that sealing off all of the leaks present in the FNGP' s water distribution network would increase the success of a Z E D program by reducing both the size of the required Z E D tteatment u-ain and the waste flow generated by said system. Given the nature of the 2 leak points identified in the water network, this assumption may not completely be valid. The loss of water from the steam ttacing lines was so minute that eliminating these leaks would have virtually no affect on a Z E D program. On the other hand, recovering wastewater apparently lost from the effluent plant, while not violating this project's boundary conditions, is likely to increase both the size of the required Z E D tteatment system and its final waste output. From the prospective of implementing a cost effective wastewater recycling program at the F N G P , there appeal's to be few benefits to closing off the 2 leak point identified in the water disttibution network. Yet for the F N G P to be recognized as a Z E D facility, the leak at the effluent plant w i l l have to be sealed, regardless of the economical consequences of this action. 56 . . A s indicated in the introduction, a. true Z E D operation would not release any waste.products into its surroundings. Given the cost, complexity and possible impracticality of such a process, the term Z E D has been somewhat watered down to indicate that no wastewater is expelled from a Z E D facility. B y this definition, the F N G P wi l l have to seal off the leak at the effluent plant as part of its transformation into a Z E D operation. A s for the steam escaping from the steam tracing lines, this water was not considered wastewater, because of its purity. Considering that evaporation ponds, spray dryers and other systems used to achieve Z E D also release water vapour, this assumption appeal's to be the industry norm. Therefore, while attempts to recapture steam venting off of the steam ttacing lines is relatively inconsequential to the Z E D project, ehminating the leak at the effluent plant is a fundamental step, albeit an uneconomical one, in establishing a Z E D program at the F N G P . Water reuse: One of the FNGP's process engineers, Shang Su, has indicated that only high quality wastewater can be directly reused, because most of the process vessels have relatively stringent water quality requirements. A s a result, identifying opportunities for wastewater reuse was limited to an examination of the plant's waste steam flows. Unfortunately, most of the uncovered steam vents were small leaks (< 5.0 m 3/day) (Table 5.3). Cost associated with collecting and reusing this steam overshadow the possible benefits (Shang Su, personal com.). One obvious exception was the loss of steam from the deaerators. Approximately 376 m 3 /day of 8 psi steam was released from these vessels (Table 5.3). Given the quantity and quality of water involved, the 8 psi steam should be condensed and reused. To evaluate the potential benefits of reusing this water, a simulation was run wherein the 8 psi steam currently venting off the deaerators was condensed and returned to the boiler feedwater hotwells. No other changes were made, and no Z E D equipment was used. When the 376 m 3/day of steam was initially returned to the water system, the ratio of raw water to 8 psi steam entering the hot lime treater fell from 855:171 to 479:171. The increased dilution of raw water with high quality condensed steam led to improved treated water quality. 57 Cleaner treated water meant cleaner boiler feedwater, which, in turn, translated into less wastewater from the boilers and the sulphur plant (Table 5.14). A t the same time, with less raw water traveling through the FESs, softener blowdown and regeneration rates also dropped. Reduction in all of these waste flows culminated in an additional saving of 72.1 m 3/day of raw water (Table 5.14). Overall, reusing the 376 m 3/day of 8 psi steam triggered changes throughout the water system, which ultimately resulted in a total raw water savings of the 448 m 3/day. Aside from affecting raw water flows, reusing the 8 psi steam also influenced the F N R discharge. Wastewater volumes leaving the polishing pond fell in response to smaller incoming blowdowns, and, with less raw water being softened, the mass of contaminants stripped out by the softeners, traveling through the distribution network, and eventually exiting the plant similarly decreased (Table 5.14). Therefore, reusing the 376 m 3/day of 8 psi steam no only resulted in a total water savings of 448 m 3/day, it also led to a smaller, less contaminated plant outflow. Clearly reusing the 8 psi steam currently discharge from the deaerators is a key step to optimizing the existing water disuibution system. Vapour traveling to the thermo-oxidizer and later released to the atmosphere may be another- potential water source ready for direct reuse (Table 5.3). Originally leached from natural gas stripping solutions, the vapour stream contains significant levels of hydrogen sulphide (H2S) and carbon dioxide (CO2) (S/P Manual). Most of the H2S is removed as elemental sulphur in the sulphur plant, while the steam, CO2 and remaining H2S move onto the thermo-oxidizer and are eventually released to the atmosphere (Fig. 2.3). If this gaseous mixture was cooled prior to its arrival at the thermo-oxidizer, condensed steam could be collected and returned to the snipping liquors. The role of the thermo-oxidizer is to transform remaining H2S into sulfur dioxide (SO2). This process is temperature dependent; good rates of conversion only occur under extremely hot conditions (i.e. > 500 °C) (S/P Manual). Although the vapour stteam could theoretically be cooled 58 and the condensing water collected, it is unclear how a drop in feed temperature mightaffeet-the H2S - SO2 conversion within the thermo-oxidizer. Furthermore, significant levels of CO2 and H2S may return with the condensed water. Contaminated reflux may reduce the effectiveness of the stripping liquids. Further research would be required to assess if water can indeed be recovered from the thermo-oxidizer feed stream without affecting the performance of either the thermo-oxidizer or the stripping solutions. Reusing this water may also pose a problem to the entire ZED project. If all of the water released through the thermo-oxidizer was reused, together with the 8 psi steam venting off of the deaerators, operational water losses would fall dangerously close to domestic wastewater production rates (i.e. 55.3 m3/day vs. 68.5 m3/day - assuming that domestic outflow is equal to half of the dirty water reaching the effluent plant - Tables 5.1 & 5.3). Most of the FNGP's steam discharges are too small to be effectively recaptured and reused. The 8 psi steam vent off of the deaerators is the obvious exception. Reusing this water should greatly reduce raw water flows and lead to a smaller, less contaminated final plant outflow. Although the vapour stream traveling from process, through the sulphur plant and eventually to the thermo-oxidizer may be another potential source of reusable water, further research is needed to be sure that reusing this water will not negatively affect other parts of the FNGP, or that reusing this steam in conjunction with the aforementioned 8 psi steam will not jeopardize the whole ZED project by lowering operational water losses below domestic system output. 5.3 Changing to a ZED System To establish a ZED program at the FNGP, wastewater generated at this facility which cannot be directly reused will have to be treated and recycled either individually or as a combined flow. There are inherent problems to dealing with each waste stream individually, as illustrated by the mechanisms needed to recycle process waters currently drained to the flare pits. Flare water, originally part of the natural gas stripping solution (Fig. 2.3), contains various hydrocarbons leached from the gas stream during processing. As a result, plant personnel have expressed strong apprehension about reusing any flare water for fear of a hydrocarbon build up within the 59 processing system, which could eventually have explosive results (Shang Su, personal com.). Installing a hydrocarbon separator would provide a means of removing the worrisome elements from the flare water. This wastewater could then be cleaned and safely poured back into the stripping solutions. Flare water flow is, however, inconsistent. It does not, as suggested in Table 5.3, continually drain to the flare pits (Shang Su, personal com.). The hydrocarbon characteristics of this water still remain to be defined. Judging by the inlet gas profile (Table 5.15), it is bound to contain a number of different contaminants, all of which are too dilute to visibly separate out of solution (personal observation). Inconsistent flow and the potential abundance of low level hydrocarbons complicate the design of a hydrocarbon separator, and cast doubts on the benefits of recycling flare water. According to plant schematics, water not vapourized during flaring travels out of the flare pits and into the effluent treatment plant. (Fig. 4.1). The effluent plant produces a relatively constant outflow (Table 5.9). The chemistry of this discharge stream has also been defined (Appendix C). The objective of optimizing the F N G P water network is to reduce the complexity of the required Z E D system by limiting the size of the F N R discharge and the demand for raw water. Although recycling the flare water back into process would help to accomplish this goal, the inconsistent production of, and (to a lesser extent) the small concentration of hydrocarbons in the flare water make this option difficult. It would be more effective to simply deal with it as part of the effluent plant outflow. Since the other wastewater discharges listed in Table 5.3 similarly suffer from inconsistent flow rates (Shang Su, personal com.), the Z E D treatment system w i l l be designed around the combined F N R discharge. 5.4 Conclusion The water flow and water chemistry data collected at the F N G P initially appeared to be of rather limited value in terms of their representative strength. Metered flow readings were average values derived from only one month's worth of data, and the mass balances were riddled with 60 inconsistencies. The January 1995 flow data were, however, generally representative of longer term trends, even i f the accuracy of some flow meters remains in question (i.e. those surrounding the FESs and effluent plant). Similarly, although the regeneration wastes from the ion-exchangers were never properly sampled, calculations based on information from several of the plant's operating manuals provided a rough characterization of the blowdown waters leaving the FESs. When the mass balances were reconstructed, most of the original discrepancies either disappeared or could be attributed to contaminants in the sampled waters (e.g.. algae in the polishing pond samples) or conditioning chemicals added to the water system. In the end, the assembled data base provided sufficient detail to continue on with the Z E D project. Opportunities for optimizing the existing water network were limited. Only two water leaks were detected; one was in the steam tracing lines, while the other appeared to be a significant loss of wastewater from the effluent plant. It is unlikely that tightening the steam tracing system wi l l have any impact on the plant's water flows, because only about 5 m 3/day of steam escapes through these vents. This represents less that 1 % of current treated water production. Recovering the wastewater lost from the effluent plant, while not violating the first boundary condition limiting this project, w i l l ultimately necessitate a larger Z E D treatment system. Waste production from this system w i l l also be larger than it would be with the current F N R discharge. Clearly, the original premise that minimizing the amount of water leaking out of the FNGP's water network would simplify the required Z E D program does not apply in this case; closing off the 2 observed leaks is unlikely to benefit the Z E D project, but the F N G P can only become a Z E D facility i f the leak at the effluent plant is eliminated. The same cannot be said for reusing some of the relatively uncontaminated steam now discharged from this facility. Although most of the steam vents are too small to warrant their recapture, the 8 psi deaerator vent is an obvious exception. Reusing the 376 mVday of lost 8 psi steam would result in a net raw water savings of 448 m 3/day. Computer simulations also indicate that the F N R discharge wi l l fall by 72 m 3/day, and that its incumbent contaminant mass wi l l be 61 reduced by 291 kg/day when this water is reused. The only other steam vent which could offer similar savings is the vapour stream released through the thermo-oxidizer. Further research is first needed to investigate i f this water can be reused without compromising either the plant's gas processing efficiency or the ability to install a Z E D system at the F N G P . Given the stringent water quality requirements of the process equipment, none of the wastewater discharged into the effluent system can be directly reused. Individually, these waters suffer from inconsistent flow rates. As a result, it is more efficient to focus on tteating and recycling these water after they combine to form the F N R discharge. A Z E D program for the F N G P was therefore designed around recycling the F N R discharge wherein no other changes were made to the water disuibution network, except that the 8 psi steam now venting from the deaerators was condensed and returned, along with other condensate, to the boiler feedwater hotwells. 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Source Rate of loss (m3/day) Destination Venting 8 psi steam off the deaerators Turbine vents: Powerhouse Process Sulphur plant Thermo-oxidizer Booster Station 12 Steam tracing Export 150 psi steam Discharge Blowdown Boilers Sulphur plant Hot lime treater Domestic backwash Softener regeneration Filter cleaning Process water 376 3.0 3.9 1.1 0.3 1.9 5.0 391 19.6 19.6 81.6 70.8 16.3 16.3 39.1 21.8 20.7 178 1.0 Atmosphere Atmosphere Atmosphere Atmosphere Atmosphere Atmosphere Atmosphere Petrosul 445 Lime pond Lime pond Lime pond Lime pond Lime pond Effluent plant Flare pits Thermo-oxidizer Sweet gas Total loss = Treated water input • 856 808 -47.9 74 Table 5.4: A mass balance on the front-end softening system. Parameter Total in a Total out3 Difference % diff. Explanation Water flow 1.45 x 10 3 1.45x 10 3 0 0 (m-Vday) Total Alkalinity 162 43.1 118 73 mis-sampled (kg/day) Solids (kg/day) Total - - - Suspended - - - - Dissolved - - - - Carbon content (kg/dav) Total 54.8 26.1 28.7 52 mis-sampled Inorganic 44.4 17.5 • 26.9 61 mis-sampled Organic 10.4 8.7 1.7 16 mis-sampled Metals Ckg/dav) Calcium 70.0 2.8 67.1 96 mis-sampled Magnesium 15.8 0.7 15.1 95 mis-sampled Sodium 154 59.6 94.1 61 mis-sampled Iron 0.5 0.7 -0.2 -50 mis-sampled Inorganics (kg/dav) Phosphates 0.1 0.1 0.0 -13 mis-sampled Chlorides 217 3.0 214 99 mis-sampled Sulfates 78.6 88.3 -9.6 -12 mis-sampled Silica 4.6 1.0 3.6 78 mis-sampled a Refer to Appendix D for calculations 75 Table 5.5: A mass balance on the lime ponds. Parameter Total i n a Total out3 Difference % diff. Explanation0 Water flow 246 238 8.0 3 (m 3/day) Total Alkalinity 51.3 17.3 34.0 66 precipitated (kg/day) Solids (kg/dav^) Total 218 610 -393 -180 FESs error ; Suspended 2.2 1.6 0.5 25 precipitated Dissolved 134 609 -475 • -354 FESs error Carbon content fkg/dav) Total 12.7 6.4 6.3 50 precipitated Inorganic 5.2 2.5 2.7 53 precipitated Organic 7.6 3.9 3.7 49 precipitated Metals Ckg/dav~) Calcium 2.5 52.7 -50.1 -1.97 x 10 3 FESs error Magnesium 0.5 4.7 -4.2 -808 FESs error Sodium 64.6 149 -84.6 -131 FESs error Iron 0.2 0.0 0.2 82 precipitated Inorganics (kg/dav) Phosphates 1.1 0.0 1.1 98 precipitated Chlorides 2.7 217 -214 -7.90 x 10 3 FESs error Sulfates 97.0 148 -50.5 -52 FESs error Silica 1.0 0.9 0.1 6 insig. difference a Refer to Appendix D for calculations b precipitated = missing mass setded out of solution within the lime ponds; FESs error = front- end softeners mis-sampled; insig. difference = insignificant difference 76 Table 5.6: A mass balance on the boilers. Parameter Total i n a Total out3 Difference % diff. Explanation13 Water flow (m-Vday) 1.03 x 104 9.85 x 103 402 4 Total Alkalinity (kg/day) 104 75.5 28.2 28 ? Solids (kg/dav) Total 840 828 12.5 1 insig. difference Suspended 7.6 3.1 4.5 59 ? Dissolved 832 824 8.0 1 insig. difference Carbon content fkg/dav) Total 67.7 63.0 4.6 7 insig. difference Inorganic 26.9 20.1 6.8 25 ? Organic 40.7 42.9 -2.2 -5 insig. difference Metals (kg/dav) Calcium 3.0 2.3 0.7 22 ? Magnesium 1.8 1.6 0.2 9 insig. difference Sodium 61.7 53.1 8.7 14 chemical add'n Iron 2.2 2.1 0.2 8 insig. difference Inorganics (kg/dav) Phosphates 0.5 1.1 -0.6 -126 chemical add'n Chlorides 2.5 2.5 0.0 0 Sulfates 67.7 79.4 -11.7 -17 chemical add'n Silica 1.5 1.6 -0.1 -3 insig. difference a Refer to Appendix D for calculations b chemical add'n = changes induced by addition BFW polishing chemicals; ? = unknown source : or sink; insig. difference = insignificant difference 77 Table 5.7: A mass balance on the sulphur plant. Parameter Total in a Total outa Difference % diff. Explanation13 Water flow (m3/day) 2.61 x 103 2.87 x 103 260 10 Total Alkalinity (kg/day) 22.0 22.9 -0.9 -4 insig. difference Solids (kg/dav) Total 197 224 -26.2 -13 insig. difference Suspended 1.5 0.5 1.0 65 ? Dissolved 196 223 -27.2 -14 insig. difference Carbon content Ckg/dav) Total 16.0 17.1 -1.1 -7 insig. difference Inorganic 6.1 5.3 0.8 13 chemical add'n Organic 10.0 11.9 -1.9 -19 ? Metals Ckg/dav) Calcium 0.7 0.6 0.1 17 ? Magnesium 0.4 0.4 0.0 4 insig. difference Sodium 11.8 18.7 -6,8 -58 chemical add'n Iron 0.5 0.5 0.0 8 insig. difference Inorganics (kg/dav) Phosphates 0.1 0.5 -0.4 -333 chemical add'n Chlorides 0.5 0.9 -0.4 -70 ? Sulfates 13.1 29.8 -16.8 -128 chemical add'n Silica 0.3 0.5 -0.1 -45 ? a Refer to Appendix D for calculations b chemical add'n = changes induced by addition BFW polishing chemicals; ? = unknown source or sink; insig. difference = insignificant difference 78 Table 5.8: A mass balance on the polishing pond. Parameter Total in a Total outa Difference % diff. Explanation15 Water flow 347 352 5 1 (m-Vday) Total Alkalinity 36.7 35.3 1.4 4 insig. difference (kg/day) Solids (kg/day) Total 922 973 -51.0 -6 insig. difference Suspended 2.9 9.5 -6.6 -232 algae Dissolved 919 964 -44.3 -5 insig. difference Carbon content (kg/dav") Total 28.4 34.3 -5.9 -21 algae Inorganic 8.9 10.1 -1.2 -13 insig. difference Organic 19.5 24.2 -4.8 -25 algae Metals Ckg/dav") Calcium 58.7 51.3 7.4 13 insig. difference Magnesium 6.6. 7.2 -0.6 -9 insig. difference Sodium 210 205 4.9 2 insig. difference Iron 0.4 0.6 -0.2 -41 algae Inorganics (kg/dav) Phosphates 0.0 0.1 -0.1 -130 algae Chlorides 239 220 18.9 8 insig. difference Sulfates 183 191 -7.6 -4 insig. difference Silica 1.7 1.8 -0.2 -10 insig. difference a Refer to Appendix D for calculations b algae = changes induced by algae in polishing pond; insig. difference = insignificant difference 79 Table 5.9: A comparison between water flow readings from January 1995 and overall averages. January Overall % Flow Path Avg. C.V.a Avg. C.V.a Monthsb Differei Reservoir - m3/day 1.0 x 103 0.44 1.1 x 103 0.39 14 9 Raw water inlet - m3/day 538 0.62 623 0.52 14 14 Treated water - m3/day 724 0.61 854 0.50 14 15 Boiler #5 - KLBH Steam production 297 0.04 285 0.13 14 -4 Blowdown 1.8 0.40 2.1 0.38 2 14 Boiler #6 - KLBH Steam production 301 0.02 276 0.23 14 -9 Blowdown 3.1 0.19 3.1 0.21 2 0 Boiler #7 - KLBH Steam production 299 0.02 281 0.12 14 -6 Blowdown 2.6 0.25 2.7 0.25 2 4 450 psi steam breakdn. - KLBH E/F trains 0.2 1.37 0.5 1.39 2 60* G/H trains 18.9 0.56 17.0 0.53 2 -11 Reboiler steam - KLBH C train - carbonate 103 0.05 106 0.18 5 3 C train - MEA 33.7 0.04 32.0 0.18 5 5 D train - carbonate 109 0.05 107 0.14 5 2 D train - MEA 35.0 0.03 33.1 0.12 5 6 E train - DEA 125 0.06 128 0.08 5 2 F train - DEA 120 0.04 126 0.08 5 5 G train -DEA 131 0.03 129 0.08 5 2 H train - DEA 127 0.05 128 0.07 5 . 1 Processed gas - mmscfd 569 0.03 569 0.04 5 Stack emissions - mmscfd 6.2 0.16 7.3 0.18 14 15* Table 5.9 (con't) January Overall % Flow Path Avg. C.V.a Avg. C.V.a Monthsb Difference Petrosul Water - m3/day 33.5 - 34.2 0.17 16 2 Steam - KLBH 1.9 - 0.6 1.04 15 -217 Effluent Plant - m3/day Incoming water 159 0.37 172 0.42 17 8 Effluent 109 0.16 148 0.30 17 26* Lime pond - m3/day 238 0.24 192 0.31 17 -24* Polishing pond - m3/day 351 0.17 329 0.25 17 7 a CV. = Coefficient of variation = standard deviation / average b Number of months over which flow readings were recorded and averaged * Significant difference between the January 1995 and overall averages (tstatistic > 1.96, p < 0.05) 81 Table 5.10: Water balances on the raw water-storage tank and front-end softeners (FESs) using metered and calculated inflow and ouflow volumes from the FESs. Metered values Calculated values Flow path (m3/day) (m3/day) Raw water storage tank Inflow Reservoir pipline 1.00 x 103 1.00 x 103 Outflows #5 unlioc cooling water 6.8 6.8 Pump sealant 6.8 6.8 Cleaning & domestic systems 137 137 Treated water system 538 859 Export to Petrosul 32.7 32.7 Inflow - outflow = 282 -38.7 Front-end softeners Inflow Raw water storage tank 538 859 8 psi steam 547 547 1.08 x 103 1.41 x 103 Outflows Hot lime treater blowdown 16.3 16.3 Ion-exchanger regeneration 39.1 39.1 Cleaning water 21.8 21.8 Stripping solution make-up 129 129 Steam venting off lime treater 360 376 Domestic filter backwash 16.3 16.3 583 599 Product water volume = 503 808 Total treated water losses3 856 856 -353 -47.9 a See Table 5.3 82 Table 5.11: Recalculated mass balance on the FNGP's front-end softening system. Parameter Total in a Total outa Difference % diff. Explanation15 Water flow 1.0 x 10 3 1.0 x 10 3 0.0 0 (m 3/day) Carbon content Inorganic (mol/day) 3.2 x 10 3 3.3 x 10 3 -95 -3 insig. difference Organic (kg/day) 8.7 6.6 2.0 23 ? Metals (kg/dav) Calcium 69.9 69.8 0.1 0 Magnesium 15.7 15.7 0.1 0 Sodium 11.0 141 -130 -1181 Ion-x regeneration Iron 0.4 0.6 -0.3 -69 ? Inorganics Ckg/dav) Phosphates 0.1 0.1 0.0 0 Chlorides 2.5 217 -215 -8554 Ion-x regeneration Sulfates 74.8 84.2 -9.4 -13 insig. difference Silica 4.5 4.5 0.0 0 a Refer to Appendix D for calculations b ? = unknown source or sink; insig. difference = insignificant difference; Ion-x regeneration = sodium chloride used to regenerate the ion-exchangers 83 Table 5.12: Recalculated mass balance on the FNGP's lime ponds. Parameter Total in a Total out a Difference % diff. Explanation13 Water flow 246 238 7.6 3 insig. difference (m3/day) Carbon content Inorganic (mol/day) 3.2 x 103 2.4 x 102 2.9 x 102 93 precipitated Organic (kg/day) 7.3 3.9 3.4 47 precipitated Metals (kg/day) Calcium 69.6 52.6 17.0 24 precipitated Magnesium 15.6 4.7 10.9 70 precipitated Sodium 148 149 -1.0 0 Iron 0.2 0.0 0.2 100 precipitated Inorganics Ckg/dav) Phosphates 1.1 0.0 1.1 100 precipitated Chlorides 217 217 0.0 0 Sulfates 97.6 148 -49.9 -51 ? Silica 4.5 0.9 3.6 80 precipitated a Refer to Appendix D for calculations b precipitated = missing mass settled out of solution within the lime ponds; ? = unknown source or sink; insig. difference = insignificant difference 84 Table 5.13: Changes that occurred in selected areas of the Fort Nelson Gas Plant's water system before and after water observed to escaping from the effluent treatment plant (E/P) was recovered. Parameter E/P leak untouched E/P leak closed Raw water flow (m 3/day) -init ial - with wastewater recycling F N R discharge flow (m 3/day) - initial - with wastewater recycling Z E D solid waste output (kg/day) - initial - with wastewater recycling 85 407 138 407 90.1 282 240 332 285 415 233 483 294 Table 5.14: Selected water flows in the Fort Nelson Gas Plant's water distribution network with and without 8 psi steam reuse. Current system 8 psi steam reused Difference Flow path (m3/day) (m3/day) (m3/day) Raw water inflow 855 407 448 8 psi steam flow to lime treater 171 171 Lost 8 psi steam 376 0.0 376 Lime treater blowdown 17.0 13.9 3.1 Ion-exchange blowdown 38.9 19.0 19.9 Boiler blowdown 80.6 54.6 26.0 Sulphur plant blowdown 69.9 46.8 23.1 Lime pond outflow 245 173 72.0 Effluent plant outflow 109 109 Polishing pond 354 282 72.0 Discharged contaminant mass 713 422 291 (kg/day) 86 Table 5.15: The average inlet gas profile for January 1994 at the Fort Nelson Gas Plant. Substance Relative abundance Nitrogen (N2) 0.0103 Hydrogen sulfide (H2S) 0.0168 Carbon dioxide (CO2) 0.1241 Organic carbon compounds: 1 - carbon elements (Cl) 0.8456 2 - carbon elements (C2) 0.0023 3 - carbon elements (C3) 0.0004 4 - carbon elements (C4) 0.0002 5 - carbon elements (C5) 0.0001 6+ - carbon elements (C6+) 0.0002 Average gas volume = 18 707 000 m3/day 87 6.0 RECYCLING TECHNOLOGY FOR THE FNGP 6.1 Re-evaluation of the Literature Review Three principle treatment technologies are available to the F N G P : distillation, ion-exchange and membrane filtration. Each systems functions optimally within a given total dissolved solids (TDS) range (Fig. 3.1). The F N R discharge had a TDS concentration of 2700 mg/L (Table 6.1). According to Figure 3.1, this level of contamination would be best treated with membrane filtration. A s previously discussed, there are two types of membrane filters: ion-selective and water permeable. E D and E D R are the best ion-selective units. R O is the most suitable water permeable membrane for the F N G P , considering the large amounts mono- and divalent ions which need to be removed from the F N R discharge before it can be reused (Table 6.1). A preliminary comparison between the 3 alternatives indicated that RO, while more sensitive to fouling than both E D and E D R , generally produces the cleanest permeate of the 3 alternatives. Finthermore, despite the higher product water output with E D and E D R , R O units are simpler and easier to operate than E D and E D R . AS a result, R O was chosen to be the best membrane filtration system. A further argument to support the use of R O at the F N G P instead of E D or E D R concerns personal safety. As most of the equipment used in R O is already in use at this facility, plant personnel are already familiar with the potential dangers associated with R O (e.g. moving parts on pumps and valves, weakened pipes bursting...). On the other hand, the driving force in electrodialysis is electricity. The abundance of electrical current and highly conductive waters in, and potentially around, E D / E D R stacks is a definite health hazard, one that does not currently exist at the plant. So, while installing a R O filter is unlikely to introduce any new hazards into the F N G P , incorporating an E D or E D R unit into the Z E D program would open plant personnel up to increased heath risks. Given the inherent advantages of R O over E D and E D R , it was selected as the most suitable treatment technology for the F N G P . 88 The R O membranes should themselves be of a spiral wound design, as this is the best of the available configurations (see Section 3.3.4). A t this stage, it makes little difference i f cellulose acetate of polyamide filters are used; they both provided the same level of treatment. When the final Z E D treatment train is developed, filter type wil l become important, because it may influence the layout of the R O pretreatment system (see Section 3.3.4). According to the literature, Z E D plants generally dispose of R O concentrates in either evaporation ponds of by solidification (see Section 3.4). Evaporation ponds are only effective in climates where ambient air conditions encourage water evaporation. This is clearly not the case in Fort Nelson (58 °N x 124 °W) for a better part of the year. Winter temperature are generally well below 0 °C, and winter can last from October to May. R O concentrates w i l l have to be disposed of by a more active approach. A brine concentrator followed up with a spray dryer or crystallizer seems to be the proven method for solidifying R O concentrates (see Section 3.4). Spray dryers produce a solid effluent, while waste products from a crystallizer still require some processing before they can be landfilled. The fine, powdery solids exiting a spray dryer can, however, be difficult to handle. Given the re- assurance of manufacturers that this is riot likely to be a problem in a properly designed system ( R C C - personal com.), and their lower costs, spray dryers appear to be the more appropriate technology to follow-up a brine concentrator as part of the Z E D program at the F N G P . Instead of using a B C S (brine concentrator - spray dryer) assembly, R O concentrates can, as suggested by some Westcoast personnel, be disposed of in a deep well. In any case, re-evaluating the available literature reveals that the most appropriate technology from the F N G P would be a reverse osmosis filtration unit followed up with a B C S assembly or a deep well . 6.2 Available Options The most suitable Z E D technology for the F N G P has been previously identified as an R O filtration unit paired up with a waste disposal system consisting of either a B C S assembly or a deep 89 well. There are, however, a number of different ways of applying this technology. The available options include: • using a 1, 2 or multi-stage R O filtration system and/or • disposing of R O concentrates in a deep well and/or • disposing of R O concentrates with a B C S assembly and/or • replacing the ion-exchangers in the front-end softening system with nanofilters (NF) to reduce solid waste production (i.e. no longer adding the large quantities of sodium chloride used to regenerate the ion-exchangers into the water network) Preliminary work with the computer simulator has also indicated that calcium, carbonate and sulphate concentrations in the F N R discharge flow are so high that, without adequate pretreatment, solids wi l l precipitate onto the R O membranes. Furthermore, regardless of the extent of pretreatment, solids wi l l continue to form in a R O system containing more than 2 successive filtering units. These findings led to the inclusion of a calcium-removal pretreatment step into the computer model, as well as the development of two additional Z E D alternatives: 1) placing the R O filters and associated disposal equipment between the hot lime treater and the ion-exchangers, rather than downstream of the.polishing pond. and/or 2) R O technology is completely excluded from the Z E D system, and only a B C S unit is used With configuration (1), effluent from the polishing pond would flow directly into the hot lime treater, which is currently in operation only 1 out of eveiy 2 or 3 days (Shang Su, personal com.). 90 Here it would mix with incoming raw water, and the combined mixture would pass into the R O assembly. The inherent advantage of this design is the use of the lime treater to partially soften the R O feedwaters, rather than building a new calcium removal process for this task. A s for option (2), the performance of a brine concentrator (B/C) is unaffected by the precipitation of calcium and magnesium salts. Instead of attaching to the sides of the vessel, solids precipitate onto seed particles introduced into the feed stream as it enters the B / C (Pankratz & Johanson 1992, Bowl in & Ludlum 1992). A s a result, a B / C can operate effectively even with highly concentrated wastewaters, hence the original intention of using a B / C to treat R O concentrates. Given the abundance of potential options, there are numerous Z E D combinations available to the plant. Initial work with the simulator indicated that any R O filtration system would be limited to two stages and that calcium pretreatment would be necessary to prevent membrane fouling even in a 1-stage set-up. With these restrictions in mind, a variety of conceptual Z E D designs were developed. 6.3 Conceptual ZED Designs Each Z E D design was developed around the FNGP's water network as it is expected to perform when the 8 psi steam released from the deaerators is recaptured and reused. Eighteen different configurations were built, and they can be classified into one of two groups based on the relative position of the Z E D equipment. 6.3.1 Back-end models In these scenarios, the required Z E D equipment was attached to the polishing pond. Recovered wastewater re-entered the water network through the front-end softening system. Ten back-end models were tested with the simulator. Four of them used 1-stage R O units, while another 4 simulations incorporated 2-stage R O filtration. The remaining 2 designs did not contain any R O 9 1 membranes; they relied solely on a B C S assembly. A l l 10 scenarios can be loosely represented by the formula: I -X (ion-exchange) or N F softening + x-stage R O + B C S or deep well disposal 6.3.2 Composite discharge designs A s opposed to the back-end models, composite discharge from the polishing pond now flowed directly into the hot lime treater, and then into downstream R O filters. Eight composite discharge solutions were developed. Four of them used 1-stage R O filtration,, while the other 4 contained a 2-stage R O process. The following equation symbolizes the different composite discharge options: I -X or N F softening + direct effluent reuse + x-stage R O + B C S or deep well disposal No composite discharge/BCS-only configurations were built, since the basis for directly reusing polishing pond effluent was to circumvent the need for an external R O pretreatment u'ain. A s no R O technology was used in the BCS-only models, this premise became irrelevant. Figure 6.1 summarizes the basic structure of all 18 Z E D designs. 92 Table 6.1: A chemical comparison of the treated water and Fort Nelson River (FNR) discharge flows. Parameter FNR discharge Treated water Total dissolved solids - mg/L 2744 279 Total organic carbon - mg/L 97.7 20.7 Inorganics: Chlorides - mg/L 627 2.4 Sulfates - mg SO4/L 543 81.9 Silica - mg S1O2/L 5.2 0.9 Metals: Calcium - mg/L 146 1.4 Magnesium - mg/L 20.6 0.5 Sodium - mg/L 584 50.5 93 Softening technology 9 4 7.0 DESIGN EVALUATION The 18 proposed Z E D designs were previously described as either back-end or composite discharge models depending on the relative position of the installed Z E D equipment. The presence or absence of a brine concentrator - spray dryer (BCS) assembly is, however, a more significant difference between the various conceptual configurations. Those solutions with a deep well in place of a B C S assembly can only transform the F N G P into a Z E D facility in the strict sense that there w i l l no longer a surface discharge from the plant to the F N R ; the water network wi l l , however, continue to generate a liquid waste, which wi l l be disposed of as a liquid. The water loop w i l l never be completely closed, unlike the B C S models which wi l l generate a solid waste. The only water that w i l l escape from a B C S design wi l l be waste steam vented from the spray dryer. Given this fundamental difference between the 18 Z E D solutions, they were evaluated separately as either B C S or deep well designs. Factors used to detemiine which are the most effective Z E D programs included cost, complexity, waste generation rates and calcium pretreatment requirements. 7.1 Simulator Performance The computer simulator was, as previously detailed, originally constructed from the water flow and water chemistry data collected at the plant. The inputted data were then replaced with formulas, transforming the static model into a predictive tool. Preliminary work with the simulator identified various bugs in the system; it occasionally crashed or did not respond as expected. A l l of the equations and the layout of the model were reviewed and, i f necessary corrected. The simulator was then repeatedly run through a series of simulations to examine i f the problems had been properly addressed. This exercise was also used to ensure that the computer's projected image of the F N G P as a Z E D facility was consistent over time and independent of previous simulations. Once the simulator passed through these tests without error, it was used to evaluate the 18 proposed Z E D configurations summarized in Figure 6.1. A t no time during the design evaluations were any major problems encountered. The program appeared to be bug free. 95 7.2 BCS Designs 7.2.1 Composite discharge models The hot lime treater successfully removed enough calcium in all four composite discharge scenarios to circumvent the need to build a calcium removal process upstream of the R O filters (Table 7.1). Product water quality from each Z E D assembly was such that, when all four systems were in full recycle, downstream softeners were no longer required. The ion-exchangers were subsequently dropped from their respective simulations (Table 7.1). The nanofilters remained in place, since they removed more than just calcium and magnesium. Using in-situ equipment to pretreat R O feedwaters required significant alterations to the existing water network (e.g. Fig . 7.1). Much larger R O and B C S units were used in all 4 composite discharge solutions compared to the simpler back-end models (Table 7.1). They were, as a result, among the most expensive of the available scenarios (Table 7.1). The composite discharge simulations also produced more waste steam than many of the other designs and roughly equivalent amounts of solid waste (Table 7.1). A s there are no significant cost or waste savings inherent in any of the 4 complex composite discharge configurations, compared to the other available options, none of them appear to be particularly well suited for the F N G P . 7.2.2 Back-end solutions: Ion-exchange vs. nanofiltration In all 3 back-end categories (i.e. 1-stage R O , 2-stage R O and BCS-only) , the scenarios containing nanofilter (NF) were at times almost identical to their respective ion-exchange (I-X) counterparts. Both models generally possessed the same size R O and/or B C S systems and produced equal volumes of waste steam, regardless of whether the Z E D equipment had just been attached or reclaimed wastewater was being recycled (Table 7.1). Calcium pretreatment demands of the 1-stage R O / N F configuration were also equivalent to those of the 1-stage R O / I - X option (Table 7.1). This was not the case in the 2-stage R O designs; the " N F " scenario continually required more calcium to be removed from R O feedwaters than its " I -X" alternative (Table 7.1). 96 There were other trends in the " I -X" and " N F " solutions which were common to all 3 groups. The " N F " options were always more expensive than the opposing " I -X" designs, due to the capital costs associated with replacing the existing ion-exchangers with nanofilters (Table 7.1). Because the front-end treatment network had to be altered to install the N F vessels (Fig. 7.2), the " N F " configurations would in reality be harder to assemble and slightly more complex to operate than their respective " I -X" alternatives. The "NF" simulations did, on the other hand, generate less solid waste than the " I -X" systems (Table 7.1). Before reclaimed wastewater was recirculated back through the plant, the difference in solid waste generation rates were significant. The "NF" models initially produced less than 2/3 of the total waste output of their respective " I -X" counterparts (Table 7.1). These savings dropped to around 13 % in both of the R O simulations after the water loops were closed (Table 7.1). The difference between the BCS-only scenarios remained above 28 % (Table 7.1). With respect to the 4 R O designs, neither " N F " configuration .illustrated.significant, sustained gains which would have suggested that they were more suitable to the F N G P than their respective " I - X " alternatives. Both " N F " systems were more expensive, more complex and, at least in the case of the 2-stage R O / N F simulations, more delicate (as illustrated by higher pretreatment demands) than either R O / I - X option (Table 7.1). Their respective B C S units produced near identical amounts of waste steam (Table 7.1). Initial solid waste savings quickly fell to only a 13 % margin of difference once wastewater recycling had started (Table 7.1). Neither R O / N F model is the best Z E D design available to the F N G P . A l l of the finding summarized in the last paragraph also apply to the B C S / N F scenario, except for solid waste output. This configuration, as stated above, continually generated less solid waste than the B C S / I - X option. Until disposal costs are properly assessed, the value of reduced wasting rates remains unclear. A s such, all 3 " I -X" solutions were still deemed to be more efficient that their " N F " counterparts. 97 7.2.3 Best of the back-end ion-exchangers Cost and complexity: The BCS-only model was the simplest of the available configurations (Table 7.1). It contained the shortest Z E D treatment system; wastewater reclamation occurred in a single vessel (Fig. 7.3), rather than in a series of separate units (Fig. 7.4), and pretreatment wi l l l ikely be limited to deaeration and p H adjustments (Fig. 7.3), instead of multiple pre-filters, pH adjustments, anti-scalant addition and possibly chlorination and/or dechlorination (Fig. 7.4). The brine concentrator (B/C) was, however, the most expensive component of any B C S design (Appendix G). The BCS-only scenario contained the largest B / C of the three " I - X " options (Table 7.1). A s a result, the simplest Z E D configuration was also the most expensive (Table 7.1). Using a 2-stage R O unit in place of a "1-stage" process increased the complexity of the overall water network. Additional pumps, pipes and p H adjustment stations were required to support the second set of membrane filters (Fig. 7.5 vs. Fig. 7.6). The resulting wastewater flow path was longer and more complicated than in either the 1-stage R O or BCS-only configurations. On the other hand, adding the second stage cut the flow of R O concentrates to the B / C by 10 % (Table 7;1). The monetary savings of using a smaller B / C were such that the 2-stage R O design was slightly cheaper than its "1-stage" counterpart (Table 7.1). It appeals that the more complex the option, the cheaper its overall capital cost. Both R O designs were cheaper than the simplest Z E D scenario, the BCS-only / I -X model. The more complex 2-stage R O simulation was similarly cheaper than the simpler R O alternative. Waste generation rates: Steam losses from the Z E D equipment were proportional to the size of the B / C . As such, the BCS-only model generated the most waste steam, while the 2-stage R O simulations produced the least (Table 7.1). Solid waste production followed a similar trend. The BCS-only scenario had the highest generation rates of the back-end/I-X solutions (Table 7.1). The 2-stage R O design produced less solid waste than its "1-stage" counterpart, although the difference between the two configurations 98 was less than 5 % (Table 7.1). While the BCS-only scenario continually generated the most solid and steam waste, and the two R O models had near identical solid waste production rates, the 2- stage R O design always vented less steam than the 1-stage R O alternative. Robustness and treated water quality: Although the robustness of a B / C has already been discussed as it pertains to pretreatment requirements, it is the cleaning ability of each Z E D system that is now being evaluated. Robustness, within this context, was assessed by observing fluctuation in product and treated water quality that occurred when given contaminant concentrations in either the raw water inflow or effluent plant outflow were changed; product water, or reclaimed wastewater, refers to water produced by the Z E D equipment, while treated water is softened water leaving the FESs. Prior to any alterations, the B C S model contained the cleanest product and treated waters, followed, in order, by the 1-stage and 2-stage R O scenarios (Tables 7.2 & 7.3). When different contaminant concentrations were doubled, reclaimed wastewater and treated water quality in the BCS-only configuration generally changed the least (Tables 7.2 & 7.3). The cleaning ability of this process was perhaps best demonsfrated when chloride and dissolved organic carbon (DOC) levels were increased. Although these changes resulted in significant increases in the abundance of both chloride and D O C in both R O designs, there was no observed deterioration in treated water quality in the BCS-only scenario (Table 7.3). Not only did the B C S - only system initially produce the cleanest water, it also proved to be the most robust of the three back-end/I-X options. The fragility of the 2-stage R O model was illustrated by its calcium pretreatment requirements. Whenever calcium, sulfate or alkalinity levels were raised, the risk of membrane fouling increased, so more calcium had to be removed in the pretreatment train (Table 7.2). The 1-stage R O design did not show the same susceptibility to salt precipitation. When the water loop was first closed, calcium pretreatment was no longer necessary (Table 7.1). A n observation not mirrored in the 2- stage alternative (Table 7.1). Subsequent changes to raw water or effluent plant chemistry rarely 99 resulted in the reinstatement of a calcium removal step (Table 7.2). The probability of salt precipitating in the 2-stage R O membranes was much higher than in the 1-stage R O vessels, illustrating the relative fragility of this system compared to its more resilient "1-stage" counterpart. Aside from being more delicate than the 1-stage R O system, the 2-stage R O configuration tended to produce the lowest quality recycled and treated waters of the three Z E D options (Tables 7.2 & 7.3). Chloride and D O C levels in the treated water were, even before any chemical alterations were made, well above current concentrations (Table 7.3). Furthermore, although some chemical manipulations caused larger relative shifts in the "1-stage R O " waters, the 1-stage R O solution always contained product and treated waters of equal or better quality than its 2-stage R O alternative (Tables 7.2 & 7.3). While the BCS-only design continually produced the highest quality waters regardless of changing water chemistry, the 1-stage R O configuration was more resilient, and generated cleaner waters, than its "2-stage" counterpart. Best design: The 1-stage R O design was less complex and more robust than the 2-stage RO-. scenario (Tables 7.1, 7.2 & 7.3). Treated and recycled water quality were similarly better in the; 1- stage R O simulation (Tables 7.2 & 7.3). The two R O systems generated roughly equivalent amounts of solid waste, although steam losses were higher in the 1-stage R O solution (Table 7.1). The 2-stage R O option was also found to be $40 000 cheaper that the 1-stage R O alternative, since it used a smaller B C S unit (Table 7.1). This was an odd finding as one would have expected a two stage R O unit to cost substantially more than a single stage R O filter. In light of the possibly questionable monetary savings associated with the more delicate and complex 2-stage R O simulation, the 1-stage R O model seems to be the better R O design. Choosing the "best" Z E D design for the F N G P thus comes down to the relative importance of cost, as both the 1-stage R O and BCS-only configurations performed successfully. The BCS-only scenario had the higher capital costs (Table 7.1). It was, on the other hand, simpler and more robust than the 1-stage R O simulation (Tables 7.1, 7.2 & 7.3). The BCS-only solution also produced better quality recycled water than the 1-stage R O alternative (Table 7.2), which lead to 100 the observed-larger-solid waste generation rates (i.e. all contaminants stripped from reclaimed wastewater were released as a solid, so the cleaner the product water, the larger the mass of removed solids) (Table 7.1). It was impossible to predict how solid waste output and recycled water quality might affect the operating costs of these two Z E D options. Therefore, within the limits of this study, it was impossible to determine which of the two configurations is the best Z E D system for the F N G P . Only further research, encompassing both bench-scale and pilot plant experiments, w i l l reveal which is the better design. 7.2.4 Conclusion Ten B C S Z E D scenarios were originally developed and evaluated. The 4 composite discharge configurations proved to be extremely bulky and complex. They were more expensive and less effective that the other 6 back-end models. None of these options were deemed to be appropriate for the F N G P . In 3 of the back-end designs, the existing ion-exchangers were replaced with nanofilters. Due to the installation costs of these new softeners, all of the " N F " scenarios were more.expensive than their respective " I -X" counterparts. There were few, i f any, benefits incurred from changing softeners that justified their relatively high costs. They were subsequently eliminated from the selection process. Comparisons between the 3 remaining ion-exchange solutions revealed that the 2-stage R O configurations was complex, fragile and produced relatively poor quality recycled water. The 1- . stage R O scenario, while a better choice than its "2-stage" counterpart, was less robust and more complicated than the BCS-only simulation. On the other hand, it was cheaper than the BCS-only system, and, with adequate pretreatment, would be just as successful at closing off the plant as the BCS-only design. Further research is needed to determine which of the two configurations, the 1- stage R O or the BCS-only option, is the best Z E D system for the F N G P . 101 7.3 Deep Well Configurations 7.3.1 Composite discharge designs Similar to the trends observed in the B C S designs, the deep well composite discharge configurations used much larger Z E D equipment than any of the back-end scenarios (Table 7.4). They were more complex than the back-end systems, and they produced far more wastewater than their back-end counterparts (Table 7.4). The sole advantage of directly reusing the polishing pond outflow waters was the elimination of an external calcium removal process (Table 7.4). Using in- situ equipment for R O pretreatment did not, however, translate into substantial cost reductions. Due to the size of the R O units required by these designs, the composite discharge solutions were far more expensive than either back-end/I-X option (Table 7.4). Even though the two composite discharge/I-X scenarios were cheaper than the back-end/NF alternatives (Table 7.4), all 4 composite discharge models were dismissed as possible Z E D designs for the F N G P . 7.3.2 Back-end solutions: Ion-exchange vs. nanofiltration R O feedwater and concentrate flows differed by at most 7 % between the back-end/NF configurations and their respective " I -X" counterparts (Table 7.4). The " N F " models were more complex and expensive than either " I -X" solution (Table 7.4). As there were no immediate benefits to replacing the existing ion-exchangers with nanofilters, neither back-end/NF design appeared to be the best Z E D solution available to the F N G P . 7.3.3 Best of the back-end ion-exchangers Cost and complexity: The 1-stage R O design was cheaper than its "2-stage" counterpart (Table 7.4). A s previously indicated, expanding a R O unit to include a second set of filters increased the complexity of the resulting water network. The 2-stage R O solution was, therefore, the more complicated and expensive of the two options (Table 7.4). 102 It is important to note that this price comparison was, as were all deep well cost analyses, limited to the capital costs of the R O membranes and associated supportive equipment (Appendix G) . The cost of a deep well was assumed to be independent of the Z E D configuration. Waste generation rates: The 2-stage R O simulation operated at a wastewater recovery rate of 60 %, while the 1-stage R O solution was limited to 50 % (Appendix F). Not surprisingly, the 1- stage R O system discharged more liquid waste to the deep well than the 2-stage R O model (Table 7.4). Robustness: A Z E D system's robustness was tested, as explained earlier, by doubling the concentrations of different constituents in the raw and effluent plant outflow waters, and observing the resulting changes in recycled and treated water quality. Prior to any alterations, the 1-stage R O simulation contained the better quality product and treated waters (Tables 7.5 & 7.6). It continued to contain the cleaner waters when contaminant levels were changed (Tables 7.5 & 7.6). The 1- stage R O option was the more robust of the two deep well solutions; it produced better quality - recycled and treated waters than its "2-stage " counterpart regardless of the changes i n water chemisuy elsewhere in the system. Best design: The 1-stage R O design was the better of the two ion-exchange scenarios. It was not only cheaper and simpler than the 2-stage R O option (Table 7.4), it was also produced higher quality treated and recycled water than the "2-stage" alternative (Tables 7.5 & 7.6). The only disadvantage of the 1-stage R O system was its higher wastewater production rates (Table 7.4), yet, given its many inherent advantages over the other deep well Z E D simulations, the 1-stage R O configuration is felt to be the best deep well solution for the F N G P . 7.3.4 C o n c l u s i o n Eight deep well models were developed and evaluated with the computer simulator. The 4 composite discharge configurations were too bulky, complex and expensive compared to the other available options. The back-end simulations with nanofilters in place of existing ion-exchangers 103 were similarly eliminated as possible Z E D solutions, as they were more complex, costly and had higher pretreatment demands than the " I -X" alternatives. Of the two remaining scenarios, the 1-stage back-end R O system was cheaper, more robust and simpler than its "2-stage" counterpart. The 1-stage R O simulation also produced the higher quality recycled and treated waters of the two models. The only advantage of the 2-stage R O configurations was its smaller wastewater stream. In any case, the 1-stage back-end R O design appears to be the best of the deep well options available to F N G P . 7.4 Evaluation Summary Information from the available literature, combined with suggestions from Westcoast personnel and the data collected from the plant, indicated that the F N G P could achieve Z E D by a number of different treatment configurations. A computer simulator was built to evaluate the effectiveness of each option. The 18 original scenarios were sub-divided into 2 categories based on their final disposal technology. Each Z E D program was then tested,and the resulting output-compared to that from the other designs within the group. The best B C S systems were the back-end, 1-stage R O and BCS-only models, which maintained an ion-exchanger in the plant's front-end softening system. They were both more robust, cost effective and simpler than the alternatives. The 1-stage R O scenario would cost around $1.61 million US dollars, while the BCS-only configuration has a price tag of around $1.79 mil l ion U S dollars. A s for the deep well designs, the best option was the back-end, 1-stage R O unit with an ion- exchanger in the raw water softening system. This model was more efficient and less complex than the other deep well configurations. The 1-stage R O system would cost approximately $101 700 US dollars, excluding the cost of the deep well. It is important to note that within every test ran, it was assumed that the 8 psi steam now venting off of the deaerators was recaptured and reused elsewhere in the water system. The cost 104 analyses reported herein were also very rudimentary in nature. They were developed from R O , N F , B C S , multi-media filter and ion-exchange unit capital costs (Appendix G); operating costs were not assessed. 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O P< CD bfi Vi 0 Pi CD bo 1 CN 3 O 00 U pq 109 ~ e* ON o ; g <N i o CN "1 £ co o CN "O CN I o >< o OO rr" c IT) O o CN I © CN •n j£ © CO I © co o CO CN "T* co • © CO rN T-J- g CN ° 'JO . p rr g CN O © © r f ^ o •*-» 3 o u 3 O T3 O I I CN o CO W) fl Vi C o CO U 110 Table 7.3: Changes in treated water quality, in the 1-stage R O , 2-stage R O and BCS-on ly back- end, B C S , ion-exchange configurations, triggered by given alterations in raw water and effluent plant outflow chemistry. Treated water chemistry3 Chemical Sulphate Sodium Chloride DOC Total C 0 3 change Model (mg/L) (mg/L) (mg/L) (mg/L) (mol/L) No changes Current system 1- stage R O 2- stage R O BCS-on ly Raw water - doubled Ca & M g b 1- stage R O 2- stage R O BCS-on ly - doubled S 0 4 & T. A l k . b 1- stage R O 2- stage R O BCS-only E/P outflow - doubled Ca & M g b 1- stage R O 2- stage R O BCS-only 81.9 50.5 2.4 6.1 3.1 x l O 4 25.3 16.6 4.2 6.0 3.6 x l O " 4 27.2 22.8 7.6 9.1 4.2 x l O " 4 25.0 25.9 0.9 2.7 4.7 x l O " 4 24.3 52.6 9.9 5.8 4.7 x l O " 4 -4% 217% 135% -4% 30% 26.1 59.6 18.3 8.7 4.7 x lO" 4 -4% 162% 140% -4% 13% 24.3 60.6 0.9 2.6 4.7 x l O " 4 -3% 134% -5% -4% 0% 47.8 16.5 4.1 6.0 1.3 x 10- 3 89% -1% -2% -1% 256% 49.8 22.7 7.5 9.0 1.3 x l O " 3 83% 0% -1% -1% 220% 49.5 10.7 0.9 2.7 7.5 x l O " 4 98% -59% -5% 0% 57% 25.3 16.6 4.1 6.0 3.45 x lO" 4 0% 0% -1% 0% -4% 27.2 22.8 7.6 9.1 4.1 x l O " 4 0% 0% -1% 0% -2% 25.0 25.9 0.9 2.7 4.7 x l O " 4 0% 0% 4% 0% 0% 111 Table 7.3 (con't) Treated water chemistry3 Chemical change Model Sulphate (mg/L) Sodium (mg/L) Chloride (mg/L) DOC (mg/L) Total C 0 3 (mol/L) -doubled SO4&.T. Alk.b 1-stage R O 26.6 16.6 4.1 6.0 9.5 x lO" 4 5% 0% -1% 0% 162% 2-stage R O 29.9 22.8 7.5 9.1 1.1 X l O " 3 10% 0% -1% 0% 160% BCS-on ly 25.0 25.0 0.9 2.7 4.7 x lO" 4 0% -3% 4% 0% 0% - doubled D O C b 1-stage R O 25.2 16.6 4.1 9.0 3.6 x l O ' 4 0% 0% -1% 49% 0% 2-stage R O 27.1 22.8 7.5 15.0 4.2 x l O " 4 0% 0% -1% 64% 0% BCS-only 25.0 25.9 0.9 2.7 4.7 x lO" 4 0% 0% -4% 0% 0% - doubled C l b 1-stage R O 25.2 16.6 5.9 6.0 3.6 x lO" 4 0% 0% 39% 0% 0% 2-stage R O 27.2 22.8 11.0 9.1 4.2 x lO" 4 0% 0% 44% 0% 0% BCS-only 25.0 25.8 0.9 2.7 4.7 x 10^4 0% 0% 4% 1% 0% 3 Calcium and magnesium treated water concentrations not shown since they were held at < 1.4 and 0.5 mg/L, repectively. b Ca = calcium, M g = magnesium, SO4 = sulphate, T .Alk . = total alkalinity, C l = cloride, Total CO3 = total carbonate content, D O C = dissolved organic carbon 112 cu ex u ea JS o Vi •3 <u "33 o cu| E o U 0 • DC ea *H C/5 1 <N fa Z T-H CN r-- vo T - H VO rf vo CN T-H o o VO 00 CN O r-H OO Os r- vo cn cn >o r-- CN T-H o o rf VO cn ON oo r> os as cn cn © O i—i i—i X X rf m o o T - H O as as rf rf O O OO CN OO rf T 1 1 1 </~) IT. o o VO CU TS . 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S i CN ON o co co r-~ co CN T - H ON m CN d g CN CO °1 g? O O NO O T-H r r co "~> S i © d CN O S i CN CO _J cs T - H VO °°. g? ^ ESS o 00 d CN 1/0 d 00 d co o o ^ • 1 0 CN CO o i CN f g= co © CO co ES o ^ ES co o ^ E£ co o 1 0 sS 2 o ON fS CO iS CN ^ O ^ 0 4 &s co NO r-H ° r̂H ĝ CN NO ^ COO ^ ES CN 00 in o CO CN g? ° rt O o ON o r-H CN O O o g o j g fi O o O PC CD bfi cd bfi «> £ CN «« cd u tf lo  T3 ~H O 1 do  1 cd < «« a on 4H 3 3 O T3 o PH CD oa cd O CC CD bfi cd -*-> I CN cd u o Q 3 3 3 O T3 O PC CD SP 0 PC CD bO cd -»-» c/3 1 CN U CD 3 3 O O PC CD 0 PC CD -*-» 1 CN 116 Table 7.6: Changes in treated water quality, in both the 1-stage and 2-stage back-end R O , deep- well , ion-exchange configurations, triggered by given alterations in raw water and effluent plant outflow chemistry. Treated water chemistry3 Chemical Sulphate Sodium Chloride DOC Total CO3 change Model (mg/L) (mg/L) (mg/L) (mg/L) (mol/L) No changes Current system 81.9 50.5 2.4 6.1 3.1 x 10- 1-stage R O 43.3 37.1 7.5 7.4 4.7 x l O " 4 2-stage R O 42.0 40.5 12.5 10.2 4.7 x lO" 4 Raw water - doubled Ca & M g b 1-stage R O 43.4 104 18.0 7.1 4.7 x 10- 4 0% 180% 141% -4% 0% 2-stage R O 41.6 106 31.4 9.6 4.7 x l O " 4 -1% 161% 151% -6% 0% - doubled S 0 4 & T. A l k b 1-stage R O 84.4 18.9 4.6 7.4 1.4 x l O " 3 95% -49% -38% 0% 190% 2-stage R O 80.0 24.6 7.9 10.1 1.4 x 10" 3 90% -39% -37% -1% 187% E/P outflow -doubled C a & M g b 1-stage R O 43.3 37.3 7.6 7.4 4.7 x 10" 4 0% 0% 1% 0% 0% 2-stage R O 42.0 40.8 12.6 10.2 4.7 x 10" 4 0% 1% 1% 0% 0% - doubled S 0 4 & T. Alk.b 1-stage R O 44.6 28.8 6.2 7.4 4.7 x l O " 4 3% -22% -17% 0% 0% 2-stage R O 44.7 24.8 7.9 10.3 2.5 x l O " 4 7% -39% -37% 1% -48% - doubled D O C b 1-stage R O 43.3 37.2 7.5 10.2 4.7 x 10"4 0% 0% 1% 38% 0% 117 Table 7.6 (con't) Chemical change Model Sulphate (mg/L) Treated water chemistry3 Sodium Chloride DOC (mg/L) (mg/L) (mg/L) Total C0 3 (mol/L) E /P outflow (con't) - doubled D O C b 2-stage R O 42.0 40.5 12.5 15.8 4.7 x l O " 4 0% 0% 0% 55% 0% -doubled C l b 1-stage R O 43.3 37.1 9.2 7.4 4.7 x l O " 4 0% 0% 22% 0% 0% 2-stage R O 42.0 40.5 15.8 10.2 4.7 x l O " 4 0% 0% 26% 0% 0% a Calcium and magnesium treated water concentrations not shown since they were held at < 1.4 and 0.5 mg/L, repectively. b Ca = calcium, M g = magnesium, SO4 = sulphate, T .Alk . = total alkalinity, C l = cloride, Total CO3 = total carbonate content, D O C = dissolved organic carbon 118 cd ••a CO OO s SH CO ^ H t—H ya 3 0 0 »H co o e o co 0 0 > CO 2 ^ TJ C 0< D —I C o c o o 0) e •c m CJ 60 Ja ^ •9 u s CJ X <D i S o a, T j 00 CO CO 3 O S3 & CO T J ? _ O O 73 <= 53 > c II C/3 U pa 00 e oo fi cd fi O E CH C im e CO 3 m 6 CD £ o O #co - II 00 c CO CJ CO X • 0 0 O s oo O co oo SH CO > CO" & 43 CJ oo 3̂ co -*-» • H 0 0 O P- s O CJ cd 3 3 in co cd CH & O ca o CO CH co 43 cd >H 3 bo O 3 O ••P oo o fi w < N cu s- 3 61) 119 Z E D system with ion-exchange softening /Product wateiM ^ tank ZED Polishing equipment Pond Raw water storage tank Hot Multi-media lime treater filters Effluent Plant FNGP Lime Ponds z I Ion- ^ *f Treated wateA exchangers J tanks J Z E D system with nanofiltration softening Raw water storage tank Hot Multi-media Cartridge pH lime treater filters filters adjustment Nanofilters = l ZED Polishing equipment Pond Lime Ponds FNGP Effluent Plant Treated water tanks 3 Figure 7.2: An illustration of the changes in equipment and flow patterns in a given ZED system using nanofiltration instead of ion-exchange softening. 120 121  Polishing Pond Pretreatment network Lime Ponds Effluent Plant FNGP Reverse Osmosis filters Solid waste Waste steam pH adjustment Product wateA tank J Figure 7.5: A simplified illustration of a 1-stage RO, BCS ZED system. 123 Polishing Pond Pretreatment network I pH adjustment Second RO stage Solid waste Waste steam Lime Ponds FNGP Effluent Plant First RO stage BCS assembly pH adjustment ^ ^ ~ ^ Z ) — • ^ P r o d u c t water\ tank J Figure 7.6: A simplified illustration of a 2-stage RO, BCS ZED system. 124 8.0 ZED IMPLEMENTATION AND IMPLICATIONS The purpose of this section is to describe the sequential changes required at the F N G P to transform it into a Z E D facility, and the rationale for, and/or consequences of, each step. STEP 1: Check the accuracy of existing flow meters The accuracy of some of the FNGP's flow meters has been called into question several times in this report. Specifically, the raw water inflow and treated water outflow meters on the FESs appeared to be mis-calibrated (see Section 5.2.1). Several Westcoast personnel have also indicated that the leak detected at the effluent plant may have been caused by incorrect flow readings instead of actual water losses (Bruce Kosugi, personal com.) These problems need to be investigated and, if necessary, corrected. A n accurate and precise water monitoring system is vital to the Z E D project. Only with such a system can the validity of the findings described herein be authenticated. Furthermore, one has to be able to properly assess water flow changes predicted to occur in Steps 2 through 7. STEP 2: Reuse the 8 psi steam venting off of the deaerators A l l of the 8 psi steam generated in the deaerators should be captured at its point of origin. If the hot lime treater is on, then the trapped 8 psi steam should be cooled with a counter-current heat exchanger using raw water heading into the hot lime treater. Using a heat exchanger to cool the 8 psi vapor w i l l ensure that raw water temperatures reach required levels without having to inject 8 psi steam directly into the lime treater. When the lime treater is "off-line", the 8 psi steam should be converted to liquid in an air-cooled condenser; the same type that is already in place at the plant (E/F Manual). To maintain current raw water dilution rates, approximately 170 m 3/day of condensed 8 psi steam should flow into the hot lime treater when it is in operation. Remaining water should be returned to the hotwells for reuse as boiler feedwater. Reusing the 8 psi steam wi l l substantially reduce both the flow of wastewater and the flux of contaminants through the lime ponds, as well as the demand for treated water make-up (see Section 125 5.2.2). If this action were carried out in isolation and the plant's wastewater continued to be discharged to the F N R , the former result may cause permit non-compliance problems. Effluent from the lime pond is used to dilute outflow waters from the effluent plant. A s the volume of available dilutant drops with 8 psi steam reuse, wastewater released to the F N R may no longer satisfy regulatory guidelines. Sealing the 8 psi steam leaks wi l l reduce raw water demands and improve the efficiency of the existing water network, hence its importance to the Z E D project. On its own, this action also has the potential to disrupt current discharge practices should the expected decrease in lime pond effluent trigger non-compliance of the plant's wastewater flow, should it continue to be discharged to the F N R . STEP 3: Collect water flow and water chemistry data Once the 8 psi vents have been sealed, plant personnel should collect water flow and chemical data to evaluate the validity of the simulator's predictions. If-the water network changes as expected, the system should continue to respond accordingly as Z E D equipment is added. On the other hand, i f the resulting flow patterns are significantly different from those predicted by the simulator, the model should be corrected and reworked to reassess the benefits of a Z E D program. STEP 4: Bench-scale and pilot-plant testing of pertinent ZED equipment Small scale testing of Z E D equipment, specifically R O membranes and a B/C, w i l l allow for a true evaluation of the robustness and resilience of the available technology to produce clean water under field conditions. These experiments wi l l also provide a better understanding of the required pretreatment trains and energy demands of each Z E D process. The resulting data can then be used to evaluate the feasibility of proceeding to full scale Z E D implementation. STEP 5: Installation of a separate domestic feed pipe on the raw water pipeline To prevent cross-contamination of domestic feedwaters with recycled wastewater a separate pipeline should be attached to the incoming raw water line. Raw water wi l l then travel directly into the domestic system without contacting reclaimed effluent. Plant personnel have already identified 126 a connection valve on the existing system where the new feedline could be connected and the equipment necessary to set-up an independent domestic feed pipe (ZED Report). S T E P 6: Attach R O filters to the water network (if applicable) Regardless of whether the chosen Z E D design is a B C S or deep well R O configuration, it may be desirable to install the R O filtration system before either a deep well or B C S assembly is purchased or installed, and to operate die plant with only the R O units attached. R O technology is cheaper than the B C S and possibly a deep well. B y running the plant with only the R O vessels attached, the plant can examine the potential effectiveness of a full-scale Z E D program before larger amounts of capital are invested in the project. Furthermore, as indicated by the deep well Z E D simulations, a smaller waste disposal system wi l l be required i f wastewater recycling starts with only the R O filters in place, since wastewater production rates wi l l drop as soon as reclaimed wastewater begins to cycle back through the plant (Tables 7.1 & 7.4). Starting the Z E D process after installing only the R O technology should, therefore, highlight any potential limitations of a full-scale Z E D program prior to purchasing the more costly final disposal equipment, as well as reduce the size and cost of these expensive systems. Operating the F N G P without a means of disposing of R O concentrates on site wi l l necessitate their discharge to the F N R . A s the R O waste stream wi l l be more concentrated than the current F N R discharge wastewater, a special temporary discharge permit may be required. Alternatively, R O concentrates could be diluted with raw water to meet current regulations, if they indeed prove to be too contaminated to be released on their own. The advantages of beginning the Z E D program with only the R O equipment in place must be considered with due respect to potential R O concentrate disposal problems. S T E P 7: Install a B C S or deep well (whichever is appropriate) Constructing a deep well wi l l complete the transformation of the F N G P to a Z E D system. Concerns about wastewater disposal now shift from the F N R to subsurface migration. Z E D implies that no liquid waste wi l l leave the F N G P . The deep well, therefore, has to be built to 127 ensure that contaminants transferred to the subsurface do not migrate off-site, a difficult and potentially expensive task. Similarly, although a B C S assembly wi l l produce a solid, rather than a liquid, waste, the waste stream wi l l still require appropriate disposal. The generated solids wi l l be water soluble; i f they are left exposed to the elements, they wi l l readily re-dissolve. Should the solid waste liquefy and drain into the F N R , the primary objective of the Z E D project (to ehminate the flow of contaminants from the F N G P into the F N R ) wi l l not have been met. Furthermore, the discharge of previously solidified contaminants into the F N R may prove to be more harmful to the river's ecosystem than the plant's current, relatively inert outflow, since the collected waste would be carried into the river during infrequent rainfalls or snow melts. The flux of material entering the river would be much higher during these storm events than it is now. For these reasons, solid waste produced from a B C S Z E D program cannot be stored in exposed above ground stock-piles. Burying the solid waste may not, on its own, constitute a sufficient disposal mechanism. Water percolating through the cover layer wi l l cause some of the underlying solids to dissolve. Unless the disposal pit has been adequately lined with an impermeable barrier, the now- contaminated water w i l l continue its downward migration until it encounters a groundwater flow and subsequently migrates off-site. A s previously indicated, off-site migration of wastewater violates the principal of a Z E D facility. Although, by regulatory standards, the solid waste generated in a B C S Z E D system would not be a hazardous or special waste, it clearly must be handled and disposed of correctly because, i f it re-dissolves and exits the F N G P compound, none of the original objectives of the Z E D project wi l l have been met. Transforming the F N G P to a Z E D facility is a relatively straight forward process. There are, however, consequences associated with such a conversion which must be considered. Final waste management is a critical issue. A l l the plant's wastewater is currently treated on-site and released to the F N R . Waste products from either a B C S or deep well Z E D design would, on the other hand, need a far more stringent disposal system. Waste management would require the constant 128 . attention of plant personnel as these wastes would be retained on site indefinitely, unlike currently treated wastewater. 129 9.0 P O T E N T I A L L I M I T A T I O N S The analyses described herein, from constructing water balances and identifying opportunities for optimization to developing a computer model and choosing the most suitable Z E D design from the resulting simulations, are all ultimately based on the original water flow and water chemistry data collected at the plant. There are potential limitations to these data and the way in which they have been used which need to be considered. First and foremost, the data may not be totally representative of the true situation at the F N G P . Some of the data were derived from assumptions and calculations rather that from actual measurements. Furthermore, only average values were utilized in this investigation. These limitations, as well as those associated with the computer simulator and the Z E D design selection process, are discussed below. 9.1 Non-Representative Numbers 9.1.1 Flow data The flow data used to characterize the F N G P initially appeared to contain some unrealistic or non-representative values, as illustrated by large discrepancies between some metered and calculated flow numbers (e.g. Table 5.10). Replacing problematic metered data with calculated values ehminated most of the inconsistencies. Plant personnel have repeatedly reviewed the constructed water balances, and it is unlikely that any serious flaws continue to exist. 9.1.2 Chemical data The inclusion of non-representative chemical values within this study is possible considering that several areas of the plant were incorrectly sampled or described by only one or two samples. A large number of inconsistencies were indeed observed in the initial mass balances (Tables 5.4 through 5.8). A re-examination of the water system indicated that water additives and other contaminating agents had been overlooked and that the characteristics of the mis-sampled waters could be estimated from information in several operational manuals at the plant. When the mass balances were reworked with this new data, a number of the earlier discrepancies disappeared. 130 The corrected data set seemed to adequately detail this facility's water chemistry. Further sampling and subsequent analyses wi l l , however, be required to fully test this hypothesis. 9.2 Sample Variability 9.2.1 Water data A l l water flows were expressed as daily averages, including inconsistent pathways such as blowdowns from the boilers, ion-exchangers and hot lime treater. This u'ansformation was necessary for the construction of the water and mass balances. Flow variability does, however, become important in sizing the required Z E D equipment. The treatment system has to be designed to handle the largest expected flows. One reason for focusing the Z E D program around the F N R discharge, instead of individual drainage points, was to avoid using costly, over designed, cleaning processes which would have to be big enough to treat large, but infrequent, feedwater volumes. The lime ponds and effluent plant produce much more consistent outflows. Nevertheless, the. volume of wastewater discharged from the plant is not constant (Table 5.9), nor, according to plant personnel, is the amount of treated water lost from the thermo-oxidizer (Shang Su, personal com.). To assess the potential impact flow variation may have on a Z E D configuration, a sensitivity analysis was performed using the back-end, 1-stage R O , B C S / I - X design. Some flow changes, such as increased treated water losses to the stack, did not significantly alter the size of the required Z E D equipment (Table 9.1), although they produced large changes elsewhere in the system (e.g. increased raw water demands and/or solid waste output). On the other hand, increasing other flow paths to account for observed variability did indeed necessitate a bigger Z E D treatment train (Table 9.1). A s illustrated by these findings, the chosen Z E D scenario wi l l have to be designed appropriately to account for water flow variability. 9.2.2 Chemical data Varying contaminant concennation wil l similarly change Z E D equipment sizing requirements. Doubling raw water calcium and magnesium content, for example, resulted in an 11 % increase in 131 R O feedwater flows in the back-end, R O , B C S / I - X models (Table 7.2). The higher calcium and magnesium levels triggered increased softener and boiler blowdowns, which then had to be treated in larger Z E D vessels. Clearly fluctuations in both water flow and water chemistry must be considered when designing the final Z E D program, as they wi l l likely affect the sizing of the required equipment. Apart from some testing on the effects of variability, this study was, in the main, restticted to initial design and comparison work, and, as such, did not incorporate actual plant variability into the analyses. 9.3 Computer Model Although all bugs appeared to have been removed from the computer simulator prior to its use in evaluating the proposed Z E D designs, there are numerous assumptions built into the simulator. They range from the obvious (e.g. chloride levels in the lime treater product waters equal those in the raw water) to the potentially erroneous (e.g. treated water from the ion-exchangers wi l l always have a calcium concentration of 1.4 mg/L). The value of the model's output is dependent on its ability to mirror the real water system; i f the simulator does not react to change the same way the actual water network would, then it has no predictive value. The realism of the model is therefore dependent on the assumptions and calculations used in its construction. If these "building blocks" are valid, then the results are valuable. The validity of the model, its output, and the resulting conclusions remain unproven at this point. In other words, although the simulator reacted as expected to given changes in the virtual water system, there is no way to know if this is how the plant's actual water network wi l l react until the same changes are made at the plant. The predictive ability of the simulator should therefore be further examined after the 8 psi steam vents are closed. A more obvious limitation of the computer model is that there is no time lag incorporated into the system. The lime ponds, effluent plant and polishing pond have hydraulic retention times of 5, 20, and 1 day(s), respectively (E/P Manual). Changes in the water distribution network would not occur as rapidly as they appear to in the model. Calcium pretreatment systems were also never 132 fully incorporated into the model. The extent of included pretreatment was the removal of calcium from R O feedwaters, and its inclusion in the R O concentrate stream. Other influences from the removal process were ignored. For example, regeneration wastes from (say) an ion-exchanger or chemical changes resulting from the use of an anti-scalant to immobilize the problematic calcium were not accounted for in the simulator. Although then- absence undoubtedly alters the absolute precision of the model , it is unlikely that the inclusion of these small missing flows, and/or chemical changes, would have changed the overall conclusions of this project. 9 . 4 ZED Design Evaluation The Z E D design selection process included a general discussion of system price. The cost of a particular Z E D program was limited to the capital investment required to purchase the key pieces of equipment, including the R O , B C S and/or N F units. R O pretreatment costs were limited to mixed- media filters and ion-exchange softeners (Appendix G). Although cartridge filters, chlorination and dechlorination stations, as well as pH adjustment stations were included in several Z E D diagrams (i.e. Figs. 7.1 & 7.4), it is unclear at this stage what pretreatment systems wi l l be needed at the F N G P beyond a mixed-media filter and inlet softener1. As a result, no cost estimates were made for these other units. They were, however, included in the illustrations to indicate that an R O pretreatment train is likely to include several different processes as suggested by Applegate (1984), Pohland (1987) and Suemoto et. al. (1994). Aside from certain parts of the hypothesized R O pretreatment trains, deep well installation, solid waste disposal and general system operating costs were never evaluated. Given that this study was initiated as a "first look" into transforming the F N G P into a Z E D facility, the reported costs should be sufficient to allow Westcoast personnel to decide i f a Z E D program is feasible and which particular option to pursue. 1 Simulator output indicated that salt precipitation in an R O unit was inevitable without inlet softening, and the presence of algae and other suspended solids in the F N R discharge w i l l necessitate a R O pre-filter. 133 9.5 Conclusion There are potential limitations inherent in this investigation. The data base on which this report is founded may contain non-representative information. The computer simulator used to test the 18 proposed Z E D designs is a yet untested model of the F N G P ' s water distribution network which instantaneously adjusts to any change, and a very rudimentary cost analysis was incorporated into the Z E D design selection process. On the other hand, plant personnel have reviewed the collected data and seems satisfied with the reported values. The simulator continued to respond as expected to changes in the plant's configuration; the pricing system used herein was sufficient to fulfill the primary objective of this project, which was to show that the F N G P can be transformed into a Z E D facility for a given amount of money. Finally, sample variability, although not taken into account during this study for previously mentioned reasons, is bound to be important in Z E D equipment sizing, as demonstrated in sensitivity analyses described above. Further research should therefore be performed prior to installing a Z E D system at the F N G P to better define water flow and water chemistry fluctuations, as well as to better assess Z E D pretreatment requirements. 134 Table 9.1: Changes to the configuration of the back-end, B C S , 1-stage R O , ion-exchange design with various flow alterations. R.W. Calcium RO B/C Waste Products flowa pretreat3 f.water3 f.water3 water solids Flow change (m3/day) (mg/L) (m3/day) (m 3/day) (m 3/day) (kg/day) Initial outlay No change 407 48.2 282 141 14.1 415 No 8 psi steam reuse 110% 146% 26% 26% 25% 68% Double T /O losses'5 48% 79% 7% 7% 7% 24% Double E/P ouflow b 0% -44% 39% 39% 39% 36% Double lime pond 47% - 81% 81% 81% 77% ull recvcle No change 138 0.0 240 120 12.0 234 No 8 psi steam reuse 275% 71.0 27% 27% 27% 103% Double T /O losses'5 130% 23.9 9% 10% 9% 42% Double E/P ouflow b -76% 0% 41% 41% 41% 55% Double lime pond -23% 0% 53% 53% 53% 16% a R . W . = raw water; Calcium pretreat. = calcium pretreatment requirements; R O f.water = feedwater flow to reverse osmosis filters; B / C f.water = feedwater flow to brine concentrator b T /O = thermo-oxidizer; E/P = effluent plant 135 10.0 CONCLUSIONS Data collected from the F N G P indicated that operational water losses are greater than domestic wastewater production rates, so the plant can theoretically become a Z E D facility. The data also showed that there are 2 leak points in the plant's water distribution network. One was in the steam tracing lines, and the second one was within the effluent plant. It is doubtful that closing off either escape route wi l l be of economic benefit to the Z E D project; the leak in the steam tracing pipes is too small to be of any consequence, and recovering wastewater lost from the effluent plant w i l l only increase the flow of domestic wastewater into a Z E D system. The increased domestic flow wi l l not jeopardize the success of a Z E D program at the plant, but it w i l l necessitate a larger treatment system to purify the water and generate a larger final waste stream than the current F N R discharge flow. Unfortunately the-FNGP-will only be recognized as a Z E D facility once the leak at the effluent plant has been eliminated. Direct wastewater reuse is limited to the 8 psi steam currently discharged from the deaerators. Collecting, condensing and reusing this water should significantly reduce raw water inflow and wastewater outflow rates, which wi l l simplify the design of the ultimate Z E D treatment train. There is, however, an inherent risk that reusing this steam may lead to the non-compliance of the F N R discharge stream, as detailed in Section 9.0 - Step 2. Due caution must be exercised i f the 8 psi steam is reused while continuing to discharge the plant's wastewaters to the F N R . Although water escaping from the thermo-oxidizer is another potentially reusable waste stream, further research is needed to detennine i f reusing this water wi l l compromise the plant's gas processing efficiency or the ability to transform this facility over to Z E D framework. Rather than tackling the remaining wastewater flows at their points of origin, the Z E D project focused on recycling the F N R discharge. Eighteen prospective Z E D designs were developed and subsequently tested with a computer simulator. The best deep well configuration was a back-end, 1-stage R O unit with an ion- 136 exchange softener in the plant's front-end softening system. This design was estimated to cost $101 700 US dollars, excluding the cost of a deep well. The best B C S models were the back-end, 1-stage R O and BCS-only options, both of which maintained an ion-exchanger in the front-end softening system. They were estimated to cost approximately $1.61 & $1.79 mill ion US dollars, respectively. Transforming the F N G P into a Z E D facility is, on its own, a simple process; the appropriate equipment just needs to be incorporated into the water system. There are, however, consequences to a Z E D program. The most important is final waste management. If a deep well solution is used, the well itself w i l l have to be build to prevent off-site migration of disposal wastes, a potentially expensive endeavor. Similarly, the'solid waste generated by a B C S assembly wi l l have to be disposed of properly to prevent any of it from resolubilizing and migrating off-site. Once a Z E D protocol is initiated, wastewater or waste solids produced at the F N G P wi l l no longer disappear with the F N R ; they wi l l remain on-site indefinitely. 137 11.0 RECOMMENDATIONS 1) Close the 8 psi steam loop regardless of whether or not a Z E D program is adopted at the plant, so long as this process can occur without disrupting current wastewater disposal practices. 2) Westcoast Energy Inc. needs to assess the viability of transforming the F N G P into a Z E D facility in light of the involved costs and final waste disposal requirements. 3) If the plant is to be transformed into a Z E D facility, implement the Z E D program as specified in Chapter 8.0. 138 REFERENCES Abdula'aly, A . I . and A . A . Chammem. 1994. Groundwater treatment in the central region of Saudi Arabia. Desalination 96: 203-214. Abdullaev, K . M . , L A . Malakhov, L . N . Poletaev and A . S . Sobol. 1992. Urban Waste Waters: treatment for use in steam and power generation. 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El l is Horwood, Toronto, Ont, Canada. 144 Z E D Report - Summary report compiled by Lloyd Scrimshaw (Westcoast Energy Inc. employee) detailing an "in-house" investigation into transforming the Fort Nelson Gas Plant into a zero- effluent discharge facility. 145 APPENDIX A WATER FLOW DATA 146 © s •33 N o S3 § .2 CJ <u -o £ c • - o —1 O j " O 1) 33 00 r - r- T t T i - T t CN _ CN o o ON l O o ON O s CN CN c n c n CN NO CN i n ON o o • O o o c n e n ON >n O O O N >n CN c n NO 00 r - i n i n NO NO c n o CN T i - c n o o i n CN c n c n c n c n CN c n CN CN c n c n c n CN CN CN c n CN CN CN CN CN c n c n c n e n c n c n c n CO _ T 3 o Q i n o o c ^ O T + i o i n o o r - ^ o o o o o o o o T t r - ~ m ^ O N O r - - [ ~ ~ N O N O i n i r ) r — i c n m m ' H C N f N l ^ t N ' H ' - l r H r H f S r - I N ^ r H r H t S ^ S oo o o T t T t N O _ . - . c n T t O N O O O N O ^ H T t N O ^ o S ^ S ^ o o T j r - O N N O o oo N O c n O N O i n ^ O i n c n c N ^ H ^ H N O c n c N ^ H t - - ' - < ( N « n O N o o 2 ; ^ - | T t - N o r - ' n N O N O o o N c n ^ H i o o N o o o o T t i n i n m , m , N O N C m m r - i n i n T t c N T t o i n O N C N c n o o r - o m r - o o r - r - ~ r - - N O > o > o r - ~ o o T t ^ T t o o o o ^ H O c N r H H r t r t r t H r t r H N C N t N C N ' t N N N N O CN O N O N 0 CN CN CN t O N CN T t N O N O O N c N c n i n c n rt M cs O N N O r~ ^ H ' )Li O N O N O N ^ - ' C N c n T t m N D r - ^ o o o N > o o C N c n T t i n N o r - o o o \ o ^ c N c o T t > n N o r - o o a N O r H r H r H r t r H C N l C N C N c N t N N l N N t N C N C n 3 S 0 0 O & X i S ° •5 o —1 DJ T 3 a, CO +-' c« Q r - ^ r ~ o O N O O \ T t c N O N c n c - > n > n c n o c - - O N O N a N T t r - - - c N C N C N c n c n c N c N c N c N c n c n ^ c n O N o c n c N O O N N O r - - - o o i n o o c N ^ T t ^ H C N c n c n • c n • c n CN <N • c n c n c n c n c o c n * — i T t 0O O NO NO c n c N CN >n o o o T t o o c n c n O N »-< c n c n c n C N C N c n r ~ T t T + c N c N c n i n O N ^ r - ^ - H VO T t -in C N T t <-! NO T t NO O O ^ \ o — i o CN CN t~-  t O N N O N O 0O N O T t o i—i O N r- O N in O c n o N c n r — O c n r ~ o o h c n v o v o M r t x o c n O O O T + O N O N T t T t l O C N ^ O N ^HrtOocNcNTtr>.Tt r~- r - - o r - c n O N c n o o o N c n O N c n o c n vOTtcn^HcncncNcNNOr-ncNcN C N g O N O N r= O N oo ON r- o o o 3 r - r ~ O N ^ - ' r — i n - — " N O O O O O T t N O O N T t T t O N O O C N ^ - , _ < ^ , - ^ _ ^ c N C N > — ' O V O N r H H H H V O M l O o o o c N O \ 0 \ o \ o t - ~ t > - r - » r-H CN CN I—I CN S E E ^ f ^ _ 4 . — H i n o N O N r - - ^ i n 1 ^ n c i o \ H O \ a \ h ^ c N c n T t i n N O r - ~ - o o o N O i-H c N c n - ^ i n N o r ~ o o o N O ^ c N c n T t i n N o r - - o o o N O ^ H H H r H r t H H r t ( S l O ) ( N N l N ( N C N t N t N ( S n C C ) cn ^ as o ON o 147 in © B o, •55 gpl S ° o -23 CJ "a CJ T j .5 o - J Cu| CJ CJ «J — TS 3 fi O Si CM B Q v o v o c N O N r ~ - a \ c o r - - c o i n r - - c N O r - ^ v o o \ c n i n c x > c N O r f ^ i n _ + r f r ^ . c o o o o r - - r f o o r f c n N O i — i i n i n < n c n m c n c n T-H OO O T -H v i i n ^ ^ c o ^ H r f r ~ r - VO o o c n ON CN ON o o ON ON o o r ~ o o c n NO i n r f o o o o o o o o ON T-H ON m CN as ON VO 0 0 T-H T H 1—1 T-H T-H •—I 1—1 1—1 CN T-H CN CN CN 1—1 i—i T-H O 0 0 r - rr, ^ c n ON OO r f £2 c n c n c n r f T - H r f O N o o « o o o r - T - i o v o o r ~ o N > o o i n t - - r ~ o o r ~ - m C N T - H C N T - H T - H T - H T - H T - H ^ H r f T -H o m r f r f C N V O OO r f < N C N ON oo i n i n h i n i / i C N C N C N c n c n c n r - C N o T -H o o o o c n c n o o \o r f v o as r- N O r f i n H r f T H cN O O ON TH CN CN CN CN H o o O N ON c o i n i n i n r f O N C N r ~ o T - H c n c n C N ^ H H T - H C N c n r f m v o r ^ o o o N CN c n r f « n v o r ^ o o o N O T H C N c n r f > n v o r - - o o o N O T H T-H T -H T-H T-H T-H T-H c N CN CN CN CN CN CN CN CN CN CO CO r f OS s es C cu S E c n s B o , •33 Ml o Sa & -fi S 0 CJ ^ s c •fi o J D- I Ct> O Si CH CJ vo C N c n T - H 0 0 c o CO CO CO v o r » r f r f ON r f o O N r - 0 0 0 0 T-H c o CN T H CN T H C N C N C N a o i n c o *n C N CO rr i n c n 0 0 i n r f H t— H m ^ r f O £ H CN f CN v o 0 0 5 CO H i n CN CN r - 0 0 0 CO 0 0 0 CN v o i n 0 r f CN i n O N V O O N r - 0 0 O N r - r f i n 0 0 i n i n 0 0 0 0 c n CO CO CO CO CO CO c o CO CO CO CO CO CO CO CO CO CN o\ VO CO CO CN CN O ON 00 C N r f vo r f r~- <N CN r f CN r - O 0O CO 0 O CN T-H CN H CN O T-H CN CN CN CN CN CN CN CN CN i n r f c o H 0 0 v o r - 0 0 v o c o r - 0 0 i n o H o C O 10 r f C - v o 0 0 c H r - r f CO CO r f v o H T-H T -H CN H H T H \ o o O c O O r f O N T H \ o o O V O C N t ~ - 0 N 0 0 T H O C N C N O l n 0 N 0 N 0 0 i n v o o c-- c o c o ON H o CN r f C O C O H CN CN CN H H H C N c n c N 0 0 os c n c n r - c n r ~ t~- o H C N T H C N c n r f i n N o r - o o o N O T H CN CO r f i n v o r - o o o N O T H C N c n r f i n v o r - o o o N O T H T H T H T H T H T H T H C N C N C N C N C N C N C N C N C N C N C O C O C J CJ Q 148 B o, •53 £o| o S3 & ̂ S ° o .52 CJ "O •is o J O J CJ 5 « E u B VI © ro e OS Q o o r r v o c ^ r ~ c N o o r - - o o r - ~ o o i n v o c N r - - - r i - C N C N r-- oo r - ~ _ _ _ • - c n o r - - o o c N c n O N V O r - - 0 » o c n c n r o o c N ( N r ^ c > o r ~ O N r ^ O O N O c x > r f o o c n c » c N r ~ c ^ C O C O C O C O C N C ^ C ^ ( N C N C N C N C O ( N o\ o - - - - - — -. . _ - o o > o r j - c 3 N r ) - v o r - ~ o o o c n r f _ C N O O N O « O r f O O O O T - H c < - ) r f s s s >0 vo < o v o o t N ' - H i r j ( n r ^ T H \ o o \ m c N O c x 3 H r> > > > O C « C N C N r N C < I ^ ^ ^ S v o O N r f O N r ^ c O T H C N V O C N C N O <—i CN cn rr v n v o r ^ o o o s O T - H C N c n - H f H H r H r H N N M N >n vo r~ oo o\ o C N C N C N C N C N c n c n C J C ea S CU 3 E ti T J c n s o CM s o CJ C J T J S c .fi o • J O J T J C J C J ro cj Q H ro 3 fi o j «2 c3 Q N l n N M l n o o ^ O ^ H r t l n c < J H ^ n O T r t O ^ ^ O m ^ O o o n ^ ^ ^ c | C ^ r i ; ^ l o ^ ^ l n c e ^ o 1 • N H o n l n ' O c ^ H n > o c ^ ^ c « ^ o c ^ n \ O H N r t o c l c n c n c N c n c n r f c n c n r f c n c n c N c N c N c N C N c n c N c N c N c N C N r f c n ^ v o a ^ O M o o o o o \ m v l N ^ m \ o H ; M M v o c , ^ a H ^ o l n ^ o ( s c ^ l o \ o ^ n o M l / l c ^ ^ l n ' ^ M l n ^ » H N l n o o ^ o o l o c ) \ r ^ l f 1 0 N O \ l O ^ r H T H C N C N C n T H T H T H ^ r H M H r H ^ r H T H T H T H ^ T H T H T - H C n C N C N C N ' - H r t < n o c n t ~ ~ r ^ o o o v o c n c N O \ r ^ r t o a i c n r f ^ H i n i n m o ^ O H ON o r - H . o t - ~ r - - r - - r - - - r - ~ r ~ < n c N ^ H ^ O O O O O O O T - I C N ^ \ 0 ^ ^ ^ t 0 0 ^ t H r t * N ° ^ H f N \ n - > ^ r t m 0 0 0 0 C N C N C N U OO OO  N N O CNcnr)-«nvor^oooN c N c n r f * n v o r ^ o o o \ 0 ' - H C N c n - s i - > n v o r - o o , - i ^ H T - H r - H r H T - H H H ^ c N C N C N C N C N C N C N C N C N C J 149 o a T t r- o NO r- VO 0 0 o oo r- oo r- T t r- r- CO oo o c- CN CN >o in 5 VO m »—1 o t-- oo r- 0 0 1—1 r- r- o os CN Os T t T t CO Ov CO Os r-- VO o CO 1 0 T t co CO CO CO T t co co co T t CO T t T t CO CO T t T t T t T t CO CO T t T t CO CO CO CO T t . 3 O oo CO 1/1 OO O "3" ^ W n l^J C J C ) V) V) ^ SL/ C ^ J C l VL^ Si-* < J T T T J " d [— V) r H C"s| '—I l O O C N O C N O O N O N O O C > C O T t < O V O c < 1 0 N T t v O C » t ^ r ^ l O C > C N C O e O C ^ S v o o c o o o c o c o w ^ i o r ^ v o v o c N c o c o v o v o o T t T t c o r ^ i o ^ O N C N CN  N ON  O N C O Tt "~ — — . — — - - — — — — - - - O OO Os Os OS CN CO vo r- vo r- Tt o OS O " O ^ H V O C O " — i C O C O O S O O T t ^ H C O T t O O O S O O C N r ~ - r - r ~ - r ~ < o v o v o « r ) C N o o o o r - - i o o c o c o r ~ CO lO Tt T t O v co IT) CO Tt CO O Si O J > o r o v o r - - o o v r ^ o v o t - - r- in vo oo m o o o r ^ O N o o o N r ^ o O O O N ' - < C S H H H r t ( S vo CN VO v o CO ON CN r- r- r- r- co o Tt Os ^ C N CO Tt *n VO C OO OS o ^ c N c o T t i o v o r ~ - o o o N O ' - < c N c o T t i o v o r ^ o o o N O ' - < 5? S3 . 3 o <U T3 •5 o, J oj ^O "S H CO 3 o O Si O J cj Q ^ • v o o ^ N m o o H n ^ . 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C N C N C N c O C N C N C N C N C N - H _ _ . . O 0 N T H r < - > r f C N 0 0 0 0 O C N r f t — N 0 c o c o r ~ > 0 > 0 r— O N r ~ T - H ( N i c N v o i r ) C N O c o > o v o i o > o r f i o o o v o r ~ - H C N C N T H T H C N C N C N C N C N T H T H T - H r t 2 O N O N r f r f s H H ° N c ^ l n N o ^ ^ R F - N H . H H » ^ c ^ n . N c M o o r n o o l £ l O H o o l n r ^ l ^ o ^ o ^ o O T H O O V O ^ ^ ^ ^ V O O N O N O N O ^ C N ^ ^ CN CN CN CN r f r - o O N r f T H C N C N C N T H T H T H T H C N C N C N C N C N T H T H ^ H C N c o r f i n v o r ~ - 0 0 O N O H C N c O r f i o v o r - o o O N O - H c N c o r f i o v o r - o o O N O H H T H T H ^ H T H T H T H T H T H C N C N C N C N C N C N C N C N C N C N C O C O 60 3 < 152 o c3 O 7 3 1 ) T 3 S c • — O 4) 1 ) CO CJ « CA o O Si O J 4> to Q CU cn CU 3 T 3 ca C J oo cn r - H ON O N O N CN m O N cn ON vo ON OO CN ON i — i in in T t CN *—1 in m >n in r- CN ON in in O N >n t- ON CN r- oo NO ON T t r - < OO r- oo OO OO cn ON CN CN CN CN T t r t cn T t T t T t T t T t cn cn cn cn T t cn T t T t cn T t T t cn cn cn cn cn T t cn cn cn cn cn inOCNCNNONOinoOCSCNNOCNTtOCNOOOONOOOOOOOOOOOONOCNNONONONO T t c > r ~ t ^ c N c N T t o p ~ c N O c N T t T t r ^ O T t ^ r ~ T t c n c n c n c n c N r - ~ o o o o cncNcNcNcncncncncNcNcNcNcntNcNcncNcncNc^cNcNcNc^ c n c n O N r - ~ c n c n r - - r - - r - - i n r - - r - c n c n ^ T t c n c n T t T t o r ^ o o r - r - - O c N O c n c n c n r - t - ~ - N O N O O N O N O N O N O N NONONOONOOOOCNCNON_,_,Cnt~-r--C--(~--NO o o o ^ o o c ^ r - ^ r ; r ; c n T t T t T t T t T t c N c N c N - H c n c n c N c N ' - H l 1 ^ ^ r o T t T t C N r ~ ^ . ^ . O N O N O N O N O N O ^ c N m T t i n N o r ~ ~ o o o N T t i n N o r ~ - o o o N O ^ c N c n T t i n N o r - o o o N O *—1 r—H < t—! T—( T—< cN C N CN C N CN CN CN CN CN CN cn > O Z CJ •5 o J OH| O Si O H 4) -t—» CO Q N O O s T t v O T t c N ' - H . ^ + c N ^ _ l ^ _ l O O O N i n O - - - • O N O O T t T t r ^ r ^ c n v o o T t H O O O O N CN 1 CN CN CN CN CN ̂  ^ r - r - CN '—1 CN CN o r-- i n m T t c n 2 o N 2 2 ^ o o o S o o r ~ - r - N O O N N r- CN i - " i - 1 CN O cn in c n c n c n c n VO (N! rH [S O N O CN NO T t rH CS (N rH rH cn ON in in in in in t n rH f ~ (S f s [V in NO CN CN r H N c n ^ i c i v O h o o o N c N c n T t i n N o t ^ o o o N O - — ' C N c n T t i n N o r ^ o o o N O ' - ^ H r H H H H H r H r H N N N C N N O N N N M n t n C J O 153 CW E s es •33 £fl S " O CJ -o •5 o —1 O H | T 3 <D O Si O J cj Q 5? M ^ o o N N t N n i n i n a v o i n H H T t r t r H i n m i r i ^ v O H H f n N O O v o o o N K ^ v o o v O ( n O H O ^ < t ' t ^ o ^ ' v t c ^ | ' ^ • ^ i • o ^ H m H H H r . ' ! t r t c < ^ o o o v o ^ O M C N C N e o c N c O T t c o c N c o e O C N C N c o e O c O c o c O T t T t T t T t i n c O T t c O c O c ^ i n i n N O i n o O O O V O N O N O i n r - - i n c N C N N O C N C N O O N O O O . — ' C O O O C S O N O C X J C X D N D C N T ^ r ^ t ^ O t ^ c o O O t ^ O O T t r ^ c N r ^ O C N t ^ O C N O c x o o o e o O O c O O O r - i O co T t T t T t • T t oo a\ o\ o j o O N o ^ ^ O N r ^ O N O N O N O N O N t ^ c ^ t ^ c n r n c n c n r ^ ^ r v i ^ + _ + S S ^ 2 ^ n - n - 2 2 2 2 2 2 2 2 ^ o N o l N O CO T t CO ^ H O _ 4 . ^ 4 . 0 N O N N O N o o o N o ^ H i o r ~ - r ~ - 0 0 N O O J T 2 r ^ H V O O O c o O O N r - - T t T t ^ ^ ON ̂  ̂  ̂ i n i n o o o o c s o o " - o o r - » _ C N C O C N C N O N O N OO > - < c N c O T t i O N O r ^ 0 0 0 N ON ON o >—i C N c o Tt u-i N O r ~ o o o N O ' - ^ c N c o T t i o N o r - o o o \ o ^ - ' H r H H f S N C N l N t N | ( N ( N N c N C N l n c n s CO O O CJ T3 C J c« CJ CJ O J -a £ c •- o —1 QJ NO CN NO CO CN O NO CO i n CN NO OO o r - CN CN CN i n NO CN r - o o NO OO i n OO NO CN NO i n o r - o CN CN ON o CN CO CO o CO C3N o r - CN o c - o o CO o CO i n CO o CN o t - - CN CN CN CN CN CN CN CN CN CN CN CN CN 1 — 1 CO CN CN CN 1 — 1 CN CN CN CN CN CN CN CN CN CN CN c O Si O J B Q i n ^ i n i n - r t T t c o o C N O N O N C N — H O N N o o o i n i n c N i n < - H C N r ^ O N ^ o o ^ - < c v i c > c N ^ o o o i n i n T t c o - H i n r - - e N T t o o i n c N c N O N c o i n ' ^ C O C O C O C O C O C O C O C O C O C N T t C O C O C O T t T t T t ^ ^ ^ ~ ^ ' ^ ~ ~ ' ~ ^ . . . _ . - - O N O N CO OO O N w in • m N O r- co C N in C O C O C O C O C O C O C O C O C O C O C O C O C O C N O N O N O N ^ ^ ^ [ ^ O N O N O N I ^ N O C O C > C ^ C O C O C O N O O N O N _ ^ O N C O C O C O C O C O H r t H S M O N ^ N ° H ' * ^ N M N M M N ' ; L ' H H O N ' H R H R H R T , * L N o o CO 0 0 N O N O O N O O ^ T t O O _ . O N T t T t N O c o T t N o i n ^ 2 ; > - H „ T t T t T t T t T t O N ^ O N O N O N O N O N o o CN CN i n N O O N N O o o T t T t T t ON Tt CO O N o o oo r- N O in CO T t T t C^ '-HCNcoTtinNor^oooN cNcoTtinNor~-oooNO^cNcoTtinNor— oo O N o H H H H H H H H H N N N N ( N | ( N ( N N t N C N l C n n CJ CJ a 154 2 u i •S3' M o 5 -22 <U T J •S o - J OJ . ' T J 13 o O Si CM -4—> Q oo oo m o n m ^ as o t— v d <~i ^ f v o o C N oo oo o r - r~- c o 0 0 in xr\ c_j; C N - t *-1 cn >o o C N r r c n c N c n o o _ r— <••; r f r f O C N t— vo „ - H oo K c n ° ° a; c n H m un o r f CN C es 5? T J c n a O CM a o u <D T J s « .a o • J O J T J • 0) O J Ct) Q =3 j? a s § g ^ i § I <8 •S 2 l a o o c N c n O N c n r h O N i n c n v o — v v , v _ , v , ^ u , . ^ \o vi T - C as r f r— cNin«nvoocN«n'-Hr-~-r-cn ( » c ^ l n r t l n N ^ l n l n ^ o \ r i ; r t ^ o c ^ c ^ ^ v o o o l n ^ • ^ ^ o o o ^ o o n l n n ^ m ^ n r n m m n M N n M n n r i r o c n m ^ n r i n c n n c n c n n ! 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CU o cu •4— c ca & _ g ca ca fc CH "5: 2 C N in cn N O r- cn r - O N c n cN ^ o V O r - H C n O N r H <n p- C N in r- oo Tt o r - < cn r - o v o oo o V O rH O N O C N r~ C N Tt CN H H C N 5 ON ^ Tt OO T t v o c n o o N « n c n o N O C N o r H T t TtNO>OTtcnTtoocn r ^ r - ,NOoocninr~-O N O O i n c n v o T t r H V j c ^ ^ ^ o l o c r ) c n v o i n i o c n T t o o c N « « H vo tv i n a Tt S g? 8 CJ to o . _ X oo O N c N l M P - h O N h C N O O i c i t S N l O O O l O C n r H O N O O r H r - H c n O O cn ca o s o cn z • H — _ o E o «H— ca ca Q r- J D ' '3 CQ CL> ca cj ,<u N O CJ CU .2 5 CQ o CQ i n I H J D "3 CQ N O c n c n r - O N N O c - - OO C N OO 00 r H r - H c n 00 r H o C N C N p O p C N in c n c n v d r-" C N c d c d C N v d v d c n c d Tt O N C N O N v d C N en C N o d c n o d Tt r - H C N c n c n O N O N O N Os O N O N O N O N O N O N O N OO O N 00 Os Os o i — i r-~ r - V O Tt Tt C N C N C N C N C N C N C N C N C N C N C N C N C N C N C N C N C N C N c n C N C N C N C N C N C N C N C N 5 Tt o q OO i n O i n O Os c n c n r—1 c n v q Tt O N Tt m r - c n v q o q CN Tt CN Tt N O i n c-; • n i n CN Tt r—< r ~ v d i n Tt o* c d O N i n Os o d d Tt c d c d CN O N CN O N O N c n CN O N O O O N o o o o o o O N Os O N o o o o OO o o o o O N Os o r - r - r - N O Tt c n c n c n CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN c n CN CN CN CN CN CN CN CN CN t> <n T t T t i n r - T?5 p o o p O p O O o O O O o o O O O o O p o O O p o o O O O O v d CN o d O N O N C-' T t CN o d O N T t T t v d CN in T t r H H d cn N O O N N O CN r-' in cn d cn cn Os o o o o o o o o o o O N Os o o OO OO OO o o OO o o OO o CN o o r- r- N O T t T t cn T t T t T t CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN cn CN CN CN CN CN CN CN CN CN CN CN p in O O p O p P p O p p p O p p O p p O O p o p O o P p p O O N v d CN o d N O N O in v d v d O N O N in N O T t r H in o d i — i O N N O cn T t in T t d v d v d N O O N T t T t t > O N O N O N O N O N O N O N O N O N O N O N Os O N O N O N o O N r H o o o r - N O N O T t m T t T t CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN cn CN CN CN CN CN CN CN CN CN CN CN in p O p O O O O p p p O O O O O o O o O in p o O p in p p p O Os in cn o d v d v d v d O N O N v d v d in cn v d cd 0 0 CN r H d in v d N O in r H o d O N o d d T t T t r- O N O N O N O N O N O N O N O N O N O N O N O N O N o O N o o CN o o tr- r- N O T t T t in T t m CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN cn CN cn en CN CN CN CN CN CN CN CN CN CN CJ c CJ o I H J U O CQ V O I H J U '3 CQ cu H - on i n I H J U '3 CQ p i n p p p p p p p p O N T t ' r ^ v d c n ' c n c n c n T t v d Tt Tt t*~* ON ON O N O N O N O N OS C J H—» ca Q H H C N cn o O o p O p o p p O O p p o p p in o in O v d cn T t r H o d rH T t en 0 0 Os Os cn in T t cn rH v d v d v d O N O N O N Os O N 0 0 O N O N O N O N O N i— i oo r- r - V O V O T t in T t T t CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN i— i CN cn T t in N O OO O N O rH CN cn T t m N O r - 0 0 O N O CN CN CN CN CN CN CN CN CN CN cn P H CJ 00 164 M .a CJ cn C3 cn £ g £ CJ r„ W K S a m <D cn 9 -a t-! r - HH _CJ "3 CO S co 1H -H1 '3 CQ r- O N — i >o o C N •n v o v o r - v o v o v o ; _ ; i > r - - r - - r - - - o o oq vq r f v> r~ i> r~ r~ r f vq v; co C N C N m co r f r f r f r f Ol CO r~ t— t— c~ o O O o o o >n O v> CN >n o r - 00 CN C~J 00 vo CN CN o VO O »—i o o o o o o o .os v> co OS C— CO o o o o o o O in r f r-O CN o o I - © r- o o o S o o o o C ; c ^ ^ g ^ g - ^ c o vo OO CO Os — H oo CN O U~i Os O vo O oo oo vo oo co r f t— v i v i as co r- V O -I V O - I CO vo vo CN OO - H cN - H oo r - r f o l 2 Os Os CN 2 2 3 CO CO 00 r-' Os tr> S £ __ " c o r f o q i n r - ^ o q v i v q vd r f H —I d d o i co ;vq o l oq CN vq v> r f —; o l p v> p p ico VO o i od r f vd r f ON r f —< r f vd vd i r f r f r f r f u - i r - o o o o O N O O V N c o c N oq H co C N vq I-- v i co v i v i v i vo o r - r- oo CO r H CN O CN r f C-; vd l> )Q d r - H CO CO co co r f r f m VI co CO CN CN CN CN o l CN <N Ol Os oq CO CO r H CO co r H CO H v j v i d vd co co r f r f r f r f co Ol o l o l CN Ol CN CN CN Ol t - H O V) r H ON CO r f vo 00 ON O C- V) _ H OO VN r- o vd 00 r H <_l r f v i CO r H C-' d CO CN ON ON d d d r f ON ON ON r f co t-~ r f VO CO co O ON t> OO ON ON ON oo oo Ol Ol Nl CO CO CO co co co co co r f co CN Ol CN Ol CN CN Ol V) p v> o vo ON p O Ol r f oq VN ON VO i—( r~ 00 vo od r H r~ NP d co V) 00 vd ON r f v i d r H d r H o i ON d oo ON CO r f CN r- co V) co Ol ON 00 o ON OO 00 t-- 00 Ol Ol co CO CO CO CO CO CO CO r f CO CN CO Ol Ol Ol Ol Ol o o o O p O O O vd co o i CO r? CO r f v i r f r f r H co (— CO Ol CN CN Ol Ol Ol CN CN O p o o o o o O O O p 00 V ) vd vd r f d ON r f ON od o o 00 o r H oo oo ON ON ON ON OO Ol d d 00 p t— o o d d ~ o o o d d ON ON Ol Ol Ol Ol CO Ol Ol o C0 o CQ v i O V i O V I O V j i o O O O O O O O O O O O O O O O O O O O O O O r f r f r f ON Vg 00 V<£ ON r f r H - H O O - C - O O C O C N c o c o r f r f c N r - O s c N c o c o r- O V ) co co V ) r f v i r f r f co r f C N O I O I O I O I O I O I O I C N C N O I C O C N C N C O C O C O C O C O C O C O C O C O - H VO CO - H - H OO 00 ON ON ON ON OO CO CN CN CN Ol CN p 00 o V) O o p o V) VI O p p O o p p o p p o o o p O p p p p O O O p ON o i r? d 00 ON ON H vd ON r H d ON 00 CO ? 00 v i r f d d r H o i o i r H 00 o i co r H r H r f r f >o r f « 0 r f r f CO CO r f Ol C~ ON CO CO V) >o >o VI r f >o 00 o ON ON ON ON ON CN o l Ol Ol Ol Ol o l Ol CN Ol o l CO Ol Ol co co co co CO co co CO CO r f CO CO CN Ol CN Ol Ol U> H H _ C J « o V; p p O p o p p p O O p p p p O O V) O p VN o r j r H v j d r j ON od CO od o i o i CO 00 od od t> l> r H ON 00 o i v i vd r f r f r f V) r f <o r f r f r f VN CO 00 o CN ON ON o ON o o oo CO Ol Ol Ol Ol CN CN CN CN CN CN CN CO CN CO Ol r H r H Ol r H Ol CN r H — H V ) t> r f U-) - H C N c o r f i o v o r - o o p o p p p p — H Os od 00 v i v i o Os Os Os ON ON CO CN CN Ol OI CN vo r - 00 Os o Ol CN Ol Ol CO CO o 165 CN ON v ^ r f oJ vq r f vq r f in in in r f in vq ^ r— vdr^rVr^r— r— r ^ r ^ r ~ PQ 2 5 ffi C} -g C M oo NO CN O v-> O O - i o r~- o i n O c n c o o O N v o O N o \ O N i n in r f O o o O V~l T - H r > o ° t o r » C O in ° m CN r f V O _ M OO o o r- o o C O o o O N O N C O r f O N O N r- o o o _ § c o o o o S 2 O v o V O OO £2 rt V ) O N O N CN *ZM > CJ ffi i§ « ft! CO r— O N V O O N O r f o o v o O N C O O O N C N r— c o o o T - H in in o o rj— r— v-> ° V I VO V~l 0 0 V O r f C O o ,—, c o o o v o r > v o ° V I r f O v o V") V O OO V O v o C N O N V O r f v o C O ° H C N C N ° c o o o r— C N O N V I r f _ i n r f v i v o v i J-X c o O C O C O O N ° J r f v o v o T - H v l o o 8 2 CJ 00 o o O T - H " v d r— v o C N 0 0 O N V I O OO T H 2 2 2 2 H 2 2 » O \ C N O c o in o q p r f r f o o ON v-> r f o i T - H o d v d ON ON _ ~ o v o o o o r - r— r— M. ffi o P3 v o c j H ca c j PQ WO O N c o r f OO O N C N C N «> H T - H C O O N O - C O O r f O N OO OO i n p o q C N C O O N OO C N r f O N O l O N OO C N C O O N C N v d o C O d o C O d O N C N C O O N C N v d O N C N d O N C N r f O N C N 3 c o o d O N C N o d o o C N O N C N O N C N C O o o C N C N O g j '—* O N J r ? 0 0 O O * • CN CN •** C N C O r f in ON o o r- C O C N o o o r f r f in v o r- p C N O N C N d O N C N 0 0 C N C O O N C N d O C O d O N O l v d 0 0 C N O N 0 0 C N O N C N r f OO C N o d o o C N C N o d 0 0 C N O N C N d OO C N d O N C N C O 0 0 C N a c ss 9 e a i »H ffi 2 « O OQ °. °. * o o r> »3j O O O N i « CN CN H p O o p o o p p O o o p O o O O O o d o i o i o d r f C N 0 0 O N c n d O N in d C N T - H O N in o o o o O N T - H o o o O N O N O N O N o o O N O N O N o o C N c o c n C N c n c n O l O l C N O l O l c n c n C N C N C N C N H4 2 'o OQ v o UH 2 '5 OQ in >-2 '3 CQ o o p o o o p O O O p O O p p O p p p O o p O O o p o O O O r f r f c n o i v d v d v d d C-" in in C O v i v d T-H C O H d C N c n d r H v d >n d H d O O r - O N O N O N O N O N O N O N o O N O N O N O N O N O N o O N O N O N O N O N O N O N OO O N O N O N O N o C N C N C N O l O l O l C N C N C N C O C N C N C N O l O l C N C O C N C N C N C N C N C N O l O l O l C N C N C N c n p o p O o o O O o O p o o O O p p p O p O O p p p O O o o O v d m i c n v d v d o d 0 0 H o d v d v d v i v i i n O N o d T - H C O T - H 0 0 T H r - - v d T H C N v d c n o o r - O N O N O N O N O N O N O N O O N O N O N O N O N O N o o OO O N O N O N O N o o O N o o O N O N O N O N o C N 0 4 C N C N C N C N C N C N C N c n C N O l C N C N C N C N C N C N C N C N O l O l O l O l C N C N C N C N C N c n o o o p p o o p p o p o O O O O p O O p p o O O o o p p p C N 0 0 C N C N o c n d o c n c n o c n c n o c n s C O v d o C O in o c n o c n C N o c n O N O N C N O s O N C N O N O N C N O N O N C N o c n v d o c n c n o c n v d O N C N v i O N C N r - ' O N C N o d O N C N v d O N C N in O N C N O N C N 8 c n N O O N C N O N C N o c n o d O c n CJ ta Q c N c n r f i n N o o - o o o N O T H c N c o r f i n N O r ^ o o c ? \ O T H 0 4 c n r f i n v o o - o o o N O H H H H H H H T - H CN CN CN CN CN CN CN O l CN CN c n > o 166 x .2 y co on O N c n c n c N O — < c n c n c » N q - H p r i _ p p o q c > Q co O O O ° o — i o o _ _ _ 2 g ~ o o S < ' " " ? o o i n rJr- vo ° 2 " " o o o o CN o o ON « D r - i i r i NO m CN c n T f o o o o N N i s O O o o ° ° CT c n O O O o o o Tf O O N CN - H C N o <rs o o o o NO c n C N o o C O H. <n NO c n M o NO NO C N ZH o o •s _ ffi r- o r- -st- o\ r~ o\ o ' -sf — c n r - o o - H i o o o Tj" NO l - ' t c o o i n N O H h o o O N T f O O 00 l > T t r- t-- Tf c n , ., . O N >n c n O N S ^ O n i n O N v O O N O \ 0 \ N * r , V D \ t h m O O n S r H O N ^ T f C » - H r H T f i n O O O Q J r H C ) O N O C n C n O ' - P t ~ - C n T f N O r - - H - H 0 O O O O O T f O O T f r H O O N O ir, c Tf g 8 _ CO co CO . _ , X co pq a. o CO NO 03 •s CO1 t o ir m '5 CQ O CQ ir PH « CO 03 B - a S rH CQ I—J r<i C CQ o p p o O O O O p O O O O O p O O O O O o O o p O O O O O O N O o d 00 N O c n CN H N O H r-H d CN i n i n c n rH o d 00 rH rH d Tf c d o d Tf i n Tf d <n d O N O N O N O N O N O N O N O N O N O N O N O N O N O N O N O N 00 00 O N O N 00 r- O N 00 O N O N O N O N O N O N C N C N C N CN CN CN CN CN CN CN C N CN CN C N CN CN CN CN CN C N CN C N CN C N C N C N C N C N C N C N O p O O O O O O p O o p O O O O o O O O o o O O p p O O O O d rH rH* 00 N O N O Tf d i n d Tf d 00 00 d Tf CN ri Tf i n d O N <n C N r-" 00 t > o d i > t"-° o o o O N O N O N O N O O N O N O N O N O N O N O N O N O N O N O N o O N 00 o o O N O N O N O N O N O N c n c n c n C N C N CN CN c n C N C N C N CN C N C N CN CN C N C N CN c n C N CN c n c n C N C N C N C N C N C N tn PH _- CQ O CQ p o p o p p p O O p p p O O O O p p O o p p o o p o r i d r H d r H r-H o d O N C N c n CN 00 d d O N O N r H • n o d NO c n c n o d c n 3 O O O O O O O N O N O O O O N O N O N O N O O O N O O O O o o c n c n c n c n c n c n CN CN c n c n c n CN C N C N C N c n c n C N c n c n c n c n c n c n c n c n o o o o rH c N c n T f i n NO r^- o o ON O r H c N c n T f i n N o r - o o o \ 0 ' - H C N c n T f i n N O i ~ ~ o o o N O r H r H - H r H r t r l r H r H r H C N C N C N C N C N C N C N C N C N C N C n C n CO CO Q 167 .a O cn ca 05 do s N H O H m s t O q ^ N O M - f - H H O H - I H O H q o N i n o q v q o q q o o t - ; a <u O O o C N iri O CN i n o r - r r O -H —c o CO O r H O s m S En - 2 8 ^ c n O O C N v o 2 o o c n VO 8 § § S 0 n ) >S ZTJ « n ° v o 2 t - O o o _ OO O s OO o o o ~ VO O ? m o _ _ _ ° v o O s v o 00 CN O s OS - ° o o o o o o in •. o • a cu cc OX) s "S Im o s V co 3 " '© J3 u cu o C es • sag c 2 | o C N v o O O s ^ M C N r f >n cn o o s t o o o c n o o c n i n i n o s VO * H I f ) r - o o - H v o ^ r - > n v o o s o »-H o s r - v o i n r ~ r f o o o o r f r - r f t> r f -H v o r f v o O s r - — i O ° m — i C N c n r f O s o o r— r H r f C- v o v o OO c n o s v o c - v o v o ' — ' O s C N O s - + V O m r H V O S OV 0 0 0O H J c n v o v o c n 1 in Os VO O c o — "5 Z U o fa o H — CS H - es Q ™ ca ffi S a m « « j X M * i i ex C H ; -3 p r f ; t > Os i c n o j O s O s r f v q p H c n i n — ; c n i n i n r - ^ r - ^ d o d d i n O O - H O O O - H c n n i c n o o O m c n n i o o o o c n Os v q p p c n c n v d o d r f c n g § o o C N o v o o o o r ^ o s ~ ~ o o o o r f 00 H ffi a m o CO v O a ca •s TS „ co s \Z ° S CO o CO 1H ffi a m o PQ c o a do V O tH a " o CQ • n H a 'S ca o o O o p p o O O o O o o p O O p O p p o p p o p O O p p p p d d i n c n v d d 00 v d c n r ~ v d 00 00 00 i n C N O s c n o d O s o d t-" v d c n c n r H H o o OS OS o o o o O s O s O s O s O s O s O s O v o o o o O O O s O s O s O s O s O s O s O s O s c n c n C N C N c n c n c n c n C N O ) C N C N C N C N C N C N c n c n c n c n c n c n C N C N C N C N C N C N C N C N C N o p O o o o p o o p O O p o O p p p o p O p o o p O p p o O O r f C N ON ON r - ' i > o d C N d 00 i n o d 00 d r H r H o d i n v d o d C N i n d d 00 o d 00 d C N o d o d O O O s O s r - O s o o o O s O s O s O s o o o O o o o r H o o o O s O s O s o O O s O s c n c n C N C N C N C N c n c n c n C N O ) C N C N c n c n c n c n c n c n c n c n c n c n c n C N C N C N c n c n C N C N o o O O o p O p p o o p O o p p O O p o o p p p O O p p p O O r f C N 00 c n v d i n O s i n c n C N O s c n c n r f i n i n C N r f r H C N v d o d c n c n c n C N i n C N c n r H O S r H r H o O o r - O 00 00 00 r - o o o o OO 00 00 OS d r H r H o O o o O o O o o O s c n c n c n c n c n C N C N C N C N C N C N C N C N C N C N C N C N c n c n c n c n c n c n c n c n c n c n c n c n c n C N ^ M ^ ^ ^ v o r - ~ c » a s 0 r t C N c n r f i n v o r ~ o o o s o - H n l c ^ H H o i c n r r i n v u r ^ c x j a s ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ i n es es 168 v q ^ r ^ v q v q p i o o q o N so\o<5sdsc^sD'sosdsDsoso'^ "O UH 2 2 K <** t o ^ o o o o NO CN Os ON 8 © £ § 2 § o o T t oo o ? 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C O C O C O O O O O V S V S C O C O O M H i n i f i ^ o s h s q c s i t N c ^ c N O s o s a s c c x t ' o s t r j c o O xt CN xt x t x t x t x t x t C O C O x t x t O O VO VS ' rS P P °. od ' O O O O CO 3 $•3 r> H co co co r~ od od od CO CO CO CO v i v i v i CO CO CO xt CN d H O- 00 vo vo vo 00 xt CN OJ OJ O xt; C~; CO CO ON _ Xt CN r H r H r H Ol' r-i CN Ol" —< « O O r i r i x t x t c o c o c o c o c o c o c o c o c o c o c o c o c o c o c o CN CN OJ O xt Oi Oi — ' r H C> 2 o o o o d d O O vs xt xt xt > OS rH* r H ' O 0 0 O Ol CO CO CO CO CO CO 1 a S3 & o £ Q vo VO C~ vd vd OS Os Os Os CSJ CO xt o> O o> o p O S O c O O S O S O S r H c O ; C N c o c o o s r ^ o - ' r - ' v d c i x t p p p p i n — ; o - _ r ^ v i o i v d r ^ v d v d o i r ^ : r H - H r H O O r H r H r H j ^ o o o o d d OS vs t— vo os os os 00 I T ) r H O - H r H vo r- r> r~ o o o o s t i n co s oo c t ( v n ^ i n c o s c o o i o r N c o s t m c i i s o j c s o T - ' - T - r - i - r r r r C s l N C V I W C S I C V I C M C S I C M C V i n C O 171 -H NO l> co ON od •> 00 00 00 r - ON o O N U o o d c < J o \ o d o \ o ' o ' r - ' t - - ' ON CN CN V) H rH CN rH rH ON O —< CO TJ- t > v i cn —' p CN c o T t rt NO - H p c » c » T t v > - H p c N N q o q - H ^ p V* CO V* r H CN* CN r H I S i n [ s QQ QX* ^ r H ON NO r i r i '—' CO CN r i r H r l r l r H r H QN C** o l c o e N C N C N C N c o c o o l o l o l o l o l c o c o o i c o c n c o c o c o c o c o c o c o c o c o e ^ .a u o a. 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O O O O V N O N O N O N O C O C O l r CJ O NO ON V ) ON ON O O O T t O O O O c ~ a 3 0 N O N O - H O N O O N O N O N r - ~ c - - t > N o o o O O O O r H r l O r H O O O O O O O O O r w o ^ t m c o N c o o i O r - w o ' t i n c o s c o c t o r w n ' t CN NO NO ON •> d d ON ON ON uo CO CO CM CNI CNI T t > o 172 O CN /-H co o oo xt r-; —< H r> CN p ^ oq v> as x t ; H « o o ^ i f l M O N v q ^ H O N i f i co v i vd c i ON d CN cn v i d d CN 06 2 od od xt xt xt vd CN H xt r— d os v i as r H O N O N O N O S O O O O O O O O O O O O O O O O O O ^ O N O N O N O N O N ^ O N O O O O O O O O O O O N O O O O C ^ O N v q x t c n o \ < r > v q v q p r ^ H H \ q v q c N o > c n ' r ~ ^ x t d < N o 6 c o ' x t d d o d c > 2 u o Q. CU X DX) s- O CO CU u o ca E Vi ct O , c o Z o fa ca H- « Q ir, p v> vd c i V) C- xt ! 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O vo ON od od S S xt d cn cn cn cn cn CN in C-; CN CN| CN vq —. i f - ; vq 00 ON CO CO © 00 HH <-H HH d d d CN *H HH CN co xt ON ON vd c i d ON r— od od od C O C O C I C O C O C O C O C O C O C N C N C O C O C O C N C N C N C N C N •a 3 vo vo vo vo vO vo r- ON vo VO VO VO vo n _ O N O N O N O N O N 2 -H r - ; v q v q v q v q O N v q i n i n i n x t o v v d v d v d v d t N v d ^ h h c c O N O N O N O N O N O N O N O N O N O N O N o q c N O N i n v q o q i n v q v q o q - H VO rH in Xt C i CN CN rH ri CN VS c N x t c o c o c o c o c o c o c o c o c o VN vq CN _ j m xt £ < N p p p p p p o i i n . N d v d v d v d v d v d _ ; v i - H O O O O O O ~ - H r~ v i oq - H in ON r- xt vd xt VO xt xt O r- C N vo vo o O CN CN ON c i VOOOr-ONrHCOo,rH - . ^ - _ - . 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C O O N O r - CM CO oq VO VO VO vo c- od vd vd vd vd ON ON ON ON ON ON ON xt uo CO h- 00 00 CN VO O N v o v q - H r - o N O N O N i n r ~ c n c n c N r H t ~ r ~ t - v i O T - w n \ t i f l ( D N c o o i o r CM CNJ CNI CNJ CNJ CNJ CVI CVI CVI CNI CO CO O CD Q 173 1 e "3 _ , T t i O C N r - O s T t r H C N . - H r t H N q i n i p i p h i n N i n ^ i n a ^ M i n q o e r H O r H O T t c n T f i o O O c n T r s u v u ' n v u i ^ r H ^ c n c n c n v u c w c j s O N O N O N O N O N O N O N O O O O O O O O O O O O O O O O O O O N O N O N O N O N O N O O O O O O ON ON ON v q ON —< cn C N Tt' ON ON ON C N C N H N ( N r t r t r t r t q O \ a O \ O N - i v o ^ M v 6 h M » d r > ^ d 6 d 6 i o ' M N N N C N l N C N ' N r t H H H H H r t CN o i cn p CN p p p p O — i -H -H H rt CN t ~ H N n « i n c < i n n m o d » o o c f l c c r » H N c n n N n c c i c n m c n N c N c N l N c i N p N O H O N oq —; C N Tf- r-i d cn d od —i — C rH O O rH O O ON t - ON p O N Tt C N p cn O N I > O N N O in Tt N O m i r i m ^ i ' w o o o ' d o d n c N i i n N B i m H d H C ^ O N C ? 0 * 0 " " " " ' 0 " " " " ' 0 0 0 0 0 ^ 0 0 0 0 Tt O NO -H H NO Cn C N C O C N rH rH o o o o o NO NO NO NO O d d d d d in in >n m m OO 'CN O I T ? 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TJ- Tt' Tt* Tt* Tt* in NO NO in in in in cn NO Tt* Tt* Tt* C"-* NO NO i n i n i n i n i n c n r---H - H v q r ^ i n r - ^ i ^ ini in >n in in C N - H ^ ^ r H - H ^ - H i n i n i n i n - H N O T t T t T t T t T t T t T t N O N O N O T t O — ' O O O — . - H - H r H - H r H - H r H O O O O O O O O O O O O O cn N O t M CN o NO d N O C ~ - - H C N T t O N l n t - ~ r H T t O N T t O N O . . - i n v o o o T t O N O N O S o ^ S S S » » S N i d i n > d i d t ^ ^ > > n T t ' i d H H A H H H A ^ H O , ^ ^ * * c > O N a o N » a a - H O O c o c n e o c o i o a \ t - ^ o o c o o o o o o o o o c N O \ r H O N r H - H C N C O O l - H r H C O T t O O O N T t r t - p O N C - O t - c o T t T t T t c n c n c o o i o o o o c N o l - ^ r H i n o c n c N c N c N c N c n c n c n c o c n c o c o T t T t P r H O O N O N i n r H O O O Tt Tt cn C N C N cn Tt Tt in rHoqcncninininONNqr-^r^ojcNini^ in cn cn* cn Tt Tt Tt* cn cn r i d o i C N C N C N CN* H d cn Tt* in in Tt cn co C N CN* Tt in" d d cococncncncncncncncnc^cncncncncncncncocncncncncnc^ 1 * t SH u Q o o o o oo oo T - c \ i c o T t m c o i ^ . c o O T -H N O N O N O O * d d d ON ON O N O N o r- CNI C O O NO c- o o o T r i n c o r ^ o o o o T - c M c O T i - m c o i ^ . cn o cn rH d rH cn o o rH rH 00 cn o T— CM CNI CO 00 in cn cn 174 g o E • ~ co co T< CO f£ O 2 v q o q c o c n v q v q o q o q i n c n r-< C N H C O p H C N c n *—< H O N C N H Tf c n C O c d c n c n *—< C N " o i Tt' c n o i o d c n Tf o d T T ' O N o i c d O N c d c d i n v d o i C N tn C N O N O \ 0 N O N 0 N 0 0 0 0 0 0 0 0 0 0 C > a N O N O N a N 0 0 a N O N 0 0 O N O v 0 0 0 0 0 0 0 0 0 0 0 0 O \ 0 0 O N 0 N V 0 v 0 O s O N O \ 0 N O N 0 N 0 N 0 v 0 N O l c N C N 0 0 c n 0 0 0 0 i n v 0 C N VO OO 0 0 0 0 OO O O T f o O O C N r H r H r H r H r H r - H r H r H V O V O V O V O O O C N C N O C N O O N N t S N N ^ M H N c n n c o m m n m n c n N N t N t N i H H r t o t m c l 42 u o a. cu OS ex e © co C O CU U O S cs C Q CS s o CA ~u z rw Im o fa cs CS Q O N n cd d oo o m oo in vo •"I - 1 "t d d st p ON c n c n Tt Tt Tt rH r-H O CN h CO 2 » ° ° O N O N O N O \ » O V O \ ° ° 2 2 2 S 0 0 V O O N ~ O N O N CN O O CN i n r~; C N p c o o d r - i c n vq C N C N C N o o r - H C N vq vq O N c o T ? ^ T f T j 5 T t c n O v o v o r H O O N v o v o o l O N — i r - r - i r ^ c n c n C n l O r H r H r - l O N O l C n c n c n c n c n c n c o T t T t 5 5 o r - c o c N t ^ O r - H r - ' c N c -C N C N c n c n c n N O N O N O N O i n ^ q q q c « » M i n i q r ; n i o i ^ q o c i n M i H q q q ^ M C A ( ' i o i o o v d o d o d o d o d r-i — i r i d c n — i — i d C N o i c n Tt i n -H* H - - i d d C N * c n Tt* o d o d c o c o c o c o c n T t T t T t c n c n c o c o c o c o c n c o c o c o c o c n c n c o c n c o c o c n ^ cn •a 1 u CN CN O J CN CN CN C N o i o i o i o i o i " ^ v o v o O N c n c n c n v q o q o q o q o q ^ ^ d d — Q S S t r O N O N O N O N v o c N c N c n o o o o o o c n c n o o o o o o o o o o o o v q i n i n rH i n c d o i c n O N Tt r - rH * CN d r-i i n r-H C N C N Tt o q C N c n i n o q C N i n i n o q o q c n C N O N _ - /-—v /--j /—, c d Tt -—H C N o i o o Tt* v d v d i n Tt C N c n c d i n c n c d c d r i i n C ^ O N O N O N O N ~ ~ ~ O N C > C > C > O \ O N O N O N O \ O N O N O N O \ O N O \ O N O N O N 0 O 0 0 c n O N T t T t r - o i v o o i n r - - i n o ) T t o c N C N c n i n c n O N O N O N O N O N O N O o r - c n o s O N C N T t T t c N c N c N c n i n i n m i n T t c n c n c n Tt C N C N Tt Tt; r-; O N Tt; Tt r - ~ r ~ o d o s O N d c N - H c n r - ~ i n o \ T t c n c n c n c N c N c n c n c n c n c n c n c N c N c n 0 0 o o CN o q 0 0 in O CN 0 0 rH o O 0 0 c n rH CN p P p t> 0 0 0 0 r l CN in c n CN* CN d n rH rH 0 0 Tt o d ON CN o i CO c n CN rH rH* rH d d o i CO r i CO c n c n c n c n Tt Tt Tt c n c n CN CN CN c n c n c n c n c n CO CO c n c n c n c n c n c n in 1 - % Si c3 Q v o N O v o d d d O N O N O N CNI C O Tf i n T f o o i n i n i n r ~ - - H T t O T f r H r H O i Tf Tf l> C N V O V O r l r l V O Q Q uo co r- co a) O r C M C O T f l O C O I ^ C O O l O i - C M C O T f L O C O h - C O CVI CNI CNI CNI CM CM CN CM CM o cu 175 .3 ro 1 e CO ^ ro cS 3 2 T j , „ Ol OO H * 5 * ^ °- o o r- o vq v-> °° ?o - Q c 'ro ui H 1 e cn *5 ro «3 ro a ffi oo oa 2 SH o H 1 V j o X ? 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"~! c i P CO r-i rH Tf' N O rH Q N V O i n oJ CN Tf O O N CO r i i—i i—i CN r i 00 V O CN CN CN CN CN CN CN T f l n i O T f c O C O O l C N C N O l O l O l C O T f T f c O C O C O C O T f c O O l O l C N O l C N C N C N C N O l C N ~ . ~ -n. , ~ ^ „ „ O r - N ( " ) ^ l l ) ( D S C O O ) O r ( v n < f l 0 1 0 S C O O ) O r - i - N n - m i l l S C O O l r r r r T - ^ r - r - r r - N N N N N N N N N N n n C J CD Q 179 s o 00 CO o 0 0 xt o v> co cn C N r-~ d Os r- xt vi xt xt i n d oi co - H xt oi d oi o ^ o ^ ^ ^ c ^ M ^ l n « m v o ^ o ^ ^ ^ c C l ( ! O M ^ ^ ^ ^ v o l n v ^ l n l n « ^ l n v ^ l n .2 j -o a - C U OS OJD CO CO CU CU o s es C O C5 c o co Z u. 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C N —< oo in _ as io , H vo o as - o r l r n ^ d -n •o a o RT C N _ vo m O N in" m- ^ ON — r^, X t OS _ • ON CN i o O ON 22 m x t • r - m x t x t O •n cn o 1 - 1 ° N _ r— cn ON d rl ^ oo H •5 Bi « O r •n x t cj i—i O r~-• ON oo vo O ON cn m x t ~- z- m in cn o P x t £ as i - ^ r H in cn _ C N n vq q O N " " m o ,B H  x t od in oo ON vo q a vo t-H o d •O 4> c oe « 2 *•* cu o , o o U 185 APPENDIX B WATER BALANCE EQUATIONS AND ASSUMPTIONS 186 GENERAL 8 psi steam balance: Raw water 8 psi steam Blowdown Given: Amount of 8 psi steam condensed in Hot Lime Treater = 20 % of raw water volume Volume of 8 psi steam generated by deaerators = 50.2 K L B H or 547 m 3 /day Treated water losses from plant (excluding 8 psi steam) = 44.1 K L B H or 480 m 3/day Hot Lime Treater blowdown =1.5 K L B H or 16.3 m 3/day x = volume of 8 psi steam condensing in teh Hot Lime Treater Then: Raw water flow =44.1 + (50.2 - x) Venting = 50.2 - x Treated water flow = (44.1 + (50.2 - x)) * 1.2 - 1.5 Since, Total incoming flow = Total outgoing flow (44.1 + 50.2 - x)+ 50.2 = (50.2 - x) + ((44.1 + 50.2 - x) * 1.2 - 1.5) + 1.5 94.3 = (94.3 - x) * 1.2 1.2x = 18.9 x = 15.7 So, 8 psi condensate = 15.7 K L B H or 171 m3/day Raw water flow = 78.9 K L B H or 859 m3/day Treated water flow = 93.2 K L B H or 1.01e3 m-Vday Venting 8 psi steam = 34.5 K L B H or 376 m3/day Venting t Hot Lime Treater Treated Water 187 #3 Hot Lime Treater blowdown: . The Water Treatment Manual (WTM) indicates that the blowdown rate = 8-10% of the recirculating sludge. By design, the sludge should be recycled at a rate of 30 gpm. Blowdown from the treater = 10% of 30 gpm = 3 gpm or 16.3 m3/day. Softener regeneration brine: Regenerating a zeolite softener requires the following water volumes (from WTM): Operation Flow rates (gpm) Time (minutes) Total flow (gallons) Backwash 495 10 4950 Brine injection 26 12 312 - dilution water 36.5 438 Brine displacement 36.5 20 730 Fast Rinse 200 30 6000 Service Rinse 200 15 3000 Grand total: 15430 These waters are discharged to the lime pond and the #3 Hot Lime Treater as detailed below: Given: Capacity of each softener = 20 000 grains/ft3 Volume of each softener =132 ft3 1 grain is = equivalent to 17.1 ppm of hardness*US gal Inlet water contains 40.5 mg/L of Ca & 1.2 mg/L of Mg Flow through all three filters = 9.31e3 Igal/h. Each unit can filter: = (20 000 grains/ft3 x 132 ft3) x 17.1 ppm*US gal/grain x 106 mg/L as CaC03 = 4.25e5 USgal of water before regeneration Time until softener needs regenerating: = 4.25e5 USgal / (9.3le3 Igal/h x 1.2 USgal/Igal x 1/2*) = 76.1 hours (* assuming only 2 filters running at any given time) Assuming: - backwash water returned to #3 treater - all other regeneration water (listed above) discharge to lime pond 188 Amount of water going back to #3 treater: = 4950 USgal/regeneration/exchanger = 65.0 USgal/h/exchanger = 195 USgal/h or 17.7 m3/day Amount of water to lime pond: = 10480 USgal/regeneration/exchanger = 138 USgal/lVexchanger = 413 USgal/h or 37.6 m3/day But using a sodium and chloride balance on the lime pond: Chloride Sodium brine concentration = 5.49e3 3.56e3 mg/L (see Appendix D) brine mass needed balance = 2.15e8 1.39e8 mg/day require flow = 3.91e4 3.91e4 L/day 39.1 m 3/day Domestic filter backwash: It was assumed that the equivalent of 3 volumes of treated water are used to backwash each of the 2 domestic.filters. They measure 30" (ID) by 60" (height), and are cleaned every 24 hours. Turbines: It was assumed that all of the turbines within the F N G P were loosing 0.1% of their incoming steam through venting. Steam tracing: It was assumed that 1% of the steam used for steam tracing escaped through leaks in the piping. Treated water cleaning: Assumed that a total of 2 K L B H or 21.8 m 3/day of treated water were used for cleaning vessels, floors ... in the 6 process trains. Water lost in sweet gas: Assumed a loss of 4 lb of water/mmscf of processed gas. The average gas production for January 1995 was 201.4 and 367.8 mmscf/day for the C /D & E / F / G / H trains, respectively. 189 Flare water: Assumed a loss of 80 lb of water/mmscf of processed gas. The average gas production for January 1995 was 201.4 and 367.8 mmscf/day for the C / D & E / F / G / H trains, respectively. Water vapour lost with the acid gas: Given: acid gas mixture contains H 2 S , C 0 2 and water % of H2S in acid gas from process = 11.2% Gas law: P A G X V = ( n H2S + n C 0 2 + n H 2 0 ) x R x T where: P ^ G = a c i d gas pressure (atm) V = acid gas volume (L) n = moles of gas R = gas constant = 0.08206 (L*atm)/(mol*K) T = temperature (Kelvins) So But and So n H 2 0 = ( P A G V / R T ) " ( n H2S + nC02> n H2s/ N AG = % H 2 S content N A G = P A G V / R T n H 2 S = ( % H 2 S ) ( P A G V / R T ) Since V is measured in scf - actual volume has been transformed into equivalent volume at 1 atm. of pressure and a temperature = 293 kelvins. 11H2S = 11.2 % x ( l atm. x 113.2 mmscfdx 28.3168 f t 3 / L ) / (0.08206 L*atm/mol*K x 293 K ) = 1.47e7 mol/day Assuming: - C 0 2 content in raw gas = 13.5 % (as indicated in Sulphur Plant Operating Manual) - A l l of the C 0 2 in the raw gas ends up on the acid gas stream 190 B y similar steps: n C 0 2 = % C 0 2 x ( P R G V R G / R T ) = 13.5 % x (1 atm. x 682.5 mmscfd x 28.3168 f t 3 /L) / (0.08206 L*atm/mol*K x 293 K ) = 1.09e8 mol/d N o w nH20 = [(1 atm. x 113.2 mmscfd x 28.3168 f t 3 /L) / (0.08206 L*atrn/mol*K x 293 K)] - (1.41 el mol/d + 1.09e8 mol/d) = 9.87e6 mol/d Mass of water: = "H20 x 18 g/mol x kg/lOOOg x 2.2046 lb/kg x day/24 h = 16300 lb/h or 178 m3/day Water formed within the Sulphur Plant: Given: mol of incoming H2S = 1.49e7 mol/d (see "water vapour in acid gas") average mass of sulphur leaving stack = 15.4 tonnes/d M o l of sulphur leaving the stack: = mass S x 1000 kg/tonne x 1000 g/kg x 1/32 mol/g = 15.4 x 1000 x 1000 x 1/32 = 4.8le5 mol/d M o l of H 2 S converted into elemental sulphur: = incoming mol - outgoing mol = 1.49e7 mol/d - 4.8le5 mol/d = 1.45e7 mol/d Conversion reaction: 2 H 2 S + S 0 2 = 3S + 2 H 2 0 So: mol H 2 0 = mol H 2 S = 1.45e7 mol/d Mass of water formed: = 1.45e7 mol/d x 18 g/mol x kg/lOOOg x 2.2046 lbs/kg x klb/lOOOlb - 23.9 K L B H or 260 m3/day 191 UNIT SPECIFIC Powerhouse Treated water to process: This value is the sum of all of the treated water demands from the 6 process trains. Process . Cleaning solution make-up: Sum of water lost in sweet gas, acid gas and to the flare pits Sulphur Plant . - Individual blowdowns: Values taken off of a schematic diagram Boiler feedwater distribution: The volumes of B F W going to the individual condensers and the reaction furnace were calculated as follows: Given: Total volume of B F W to Sulphur Plant = 160 K L B H or 1.74e3 m 3/day 5 condensers produce 37.2 K L B H or 378' m 3/day of condensate 15 psi condensers produce 34.7 K L B H or 378 m 3/day of condensate Reaction furnace blowdown = 2.0 K L B H or 21.8 nvtyday Blowdown from #1 condensers =1.5 K L B H or 16.3 m 3 /day Blowdown from #2 condensers = 3.0 K L B H or 32.7 m 3 /day 150 psi steam to Petrosul = 1.8 K L B H or 19.7 m 3/day 45 psi steam from #2 condenser = 41.0 K L B H or 446 m 3 /day B F W to reaction furnace: = 5 psi condensate + Petrosul + blowdown + venting = 37.2 + 2 .0+1.8 = 41.0 K L B H or 446 m3/day B F W to #2 condensers: = 15 psi condensate + blowdown + 45 psi steam = 34.7 + 3.0 + 41.0 = 78.7 K L B H or 857 m3/day B F W to #1 condensers: = 160 - (B.F.W. to #2 condensers + B . F . W . to reaction furnace) = 160- (78.7 +41.0) 192 = 40.3 K L B H or 438 m3/day 45 psi steam from #1 condensers: = B . F . W . to #1 condensers - blowdown = 40.3 - 1.5 = 38.8 K L B H or 422 m3/day Effluent Plant: Dirty raw water: Assumed that 137 of the 159 incoming units was dirty raw water used either for cleaning within the domestic system. Sour water: Assumed that the amount of sour water traveling to the effluent plant is negligible 193 APPENDIX C WATER CHEMISTRY DATA 194 Fort Nelson River No-Name Creek Date of sample collection Parameter March May June * July Avg. April July Avg. General pH 7.8 7.3 7.6 7.7 7.6 7.6 7.8 7.7 Conductivity 571 300 430 358 415 393 405 399 Alkalinity P M 141 76.0 114 106 93.0 155 Total 141 76.0 114 106 109 93.0 155 116 Solids Total 380 266 5365 734 1686 659 442 880 Suspended 1.25 174 4316 512 1251 395 206 591 Dissolved 379 92.2 1049 222 435 265 236 289 Carbon content Total 35.9 30.9 32.8 34.4 33.5 28.4 63.7 40.0 Organic 0.5 12.1 3.8 8.3 6.2 5.5 25.2 11.3 Inorganic 35.4 18.8 29.0 26.1 27.3 22.9 38.5 28.7 Metals Calcium 73.8 38.2 114 54.9 70.1 45.0 61.1 57.8 Magnesium 23.6 8.2 29.5 13.6 18.7 10.8 14.2 14.4 Sodium 11.4 7.6 6.1 5.1 7.6 9.0 5.4 6.8 Iron 0.13 2.46 28.0 5.03 8.90 6.36 3.14 5.86 Inorganics Phosphates 0.05 0.05 0.07 0.08 0.06 0.05 0.05 0.06 Chlorides 2.2 1.7 1.0 1.3 1.6 1.6 2.4 1.7 Sulphates 129 43.6 82.8 49.0 76.0 62.9 21.0 52.2 Silica 4.1 2.8 3.8 3.6 3.6 0.6 7.5 3.8 Units : pH = pH units Conductivity = |J.S/cm @ 25 C Alkalinity = mg/L as CaC03 Solids — Carbon content — mg/L Metals — Phosphates = mg of P/L Chlorides = mg of Cl/L Sulphates = mg of S04/L Silica = mg of Si02/L June sample collected after heavy rainfall 195 Raw water header Sample dropped from final data set Date of sample collection ^ Parameter 3-May 8-May 10-May 15-May 17-May 24-May 12-Jul Avg. General pH 8.0 7.8 8.0 7.9 7.9 8.0 7.6 7.9 Conductivity 571 666 658 476 489 518 792 563 Alkalinity P i M 202 201 200 169 158 155 139 Total 202 201 200 169 158 155 139 181 Solids Total 452 419 241 564 345 354 709 396 Suspended 9.88 4.02 4.67 4.60 14.33 0.56 1.91 6.34 Dissolved 443 414 237 559 331 353 707 389 Carbon content Total 60.1 61.3 62.0 46.4 72.0 52.6 170 59.1 Organic 9.2 9.1 9.8 8.3 9.5 9.8 135 9.3 Inorganic 50.9 52.2 52.2 38.1 62.5 42.8 35.0 49.8 Metals Calcium 97.3 90.3 92.2 70.9 68.4 68.4 66.7 81.3 Magnesium 21.4 21.0 20.0 16.7 15.1 15.5 16.9 18.3 Sodium 17.7 12.1 11.6 10.6 11.2 11.8 37.4 12.5 Iron 0.39 0.40 0.38 0.31 0.67 0.21 0.42 0.39 Inorganics Phosphates 0.05 0.05 0.05 0.05 0.05 0.05 0.11 0.05 Chlorides 3.5 2.1 2.0 3.6 3.9 2.1 82.7 2.9 Sulphates ,81.6 100.3 100.8 81.1 77.5 79.3 85.9 86.8 Silica 5.3 5.3 5.9 5.0 5.3 4.5 3.1 5.2 Units : pH = pH units Conductivity = uS/cm @ 25 C Alkalinity = mg/L as CaC03 Solids — Carbon content — mg/L Metals — Phosphates = mg of P/L Chlorides = mg of Cl/L Sulphates = mg of S04/L Silica = mg of Si02/L 196 Reservoir water Sample dropped from final data set ^ Date of sample collection Parameter 3-May 8-May 10-May 15-May 17-May 24-May 12-Jul Avg. General pH 7.5 No No No No 8.2 7.9 8.1 Conductivity 89.6 Sample Sample Sample Sample 504 523 514 Alkalinitv P I M 37.0 151 136 Total 37.0 151 136 144 Solids Total 92.5 331 297 314 Suspended 1.27 4.79 1.85 3.32 Dissolved 91.2 327 296 311 Carbon content Total 10.6 51.3 45.1 48.2 Organic 2.8 10.4 11.2 10.8 Inorganic 7.8 40.9 33.9 37.4 Metals Calcium 15.4 65.2 62.6 63.9 Magnesium 2.8 15.2 16.3 15.8 Sodium 2.6 12.0 11.1 11.5 Iron 0.10 0.14 0.20 0.17 Inorganics Phosphates 0.05 0.05 0.08 0.06 Chlorides 0.5 2.3 1.3 1.8 Sulphates 13.2 87.8 69.8 78.8 Silica 1.0 4.5 3.6 4.0 Units : pH = pH units Conductivity = |iS/cm @ 25 C Alkalinity = mg/L as CaC03 Solids — Carbon content — mg/L Metals — Phosphates = mg of P/L Chlorides = mg of Cl/L Sulphates = mg of S04/L Silica = mg of Si02/L 197 Treater system outlet Date of sample collection Parameter 3-May 8-May. 10-May 15-May 17-May 24-May Avg. General pH 9.4 10.1 9.8 10.4 No 11.0 9.9 Conductivity 229 365 324 327 Sample 1124 311 Alkalinity P 7.0 16.5 10.5 23.5 186 M 14.5 7.5 20.5 11.0 140 Total 21.5 24.0 31.0 34.5 326 27.8 Solids Total 222 201 54 420 541 288 Suspended 23.4 3.14 1.52 2.19 14.5 8.95 Dissolved 199 198 52 418 527 279 Carbon content Total 9.8 8.8 11.4 2.4 52.8 20.7 Organic 5.8 5.2 5.4 5.3 8.1 6.1 Inorganic 4.0 3.6 6.0 i l l l l l l l l 44.7 14.6 Metals Calcium 1.5 0.2 0.1 0.1 5.0 1.4 Magnesium 1.2 0.3 0.1 0.3 0.5 0.5 Sodium 45.2 51.5 54.8 50.6 180 50.5 Iron 0.04 1.78 0.35 0.86 0.04 0.61 Inorganics Phosphates 0.05 0.11 0.05 0.06 0.06 0.07 Chlorides 1.7 2.1 2.1 2.4 3.7 2.4 Sulphates 102 84.0 79.6 68.8 74.9 81.9 Silica 0.5 0.2 1.8 0.2 1.8 0.9 Units : pH = pH units Conductivity = |J.S/cm @ 25 C Alkalinity = mg/L as CaC03 Solids — Carbon content — mg/L Metals — Phosphates = mg of P/L Chlorides = mg of Cl/L Sulphates = mg of S04/L Silica = mg of Si02/L = dropped samples 198 Softener regeneration brine Hot Lime Treater Parameter 3-May Date of sample collection 8-May 10-May 15-May 17-May 24-May Avg. 12-Jul General p'H •11.2 11.1 11.4 10.4 No 11.3 11.1 9.7 Conductivity 1324 1184 2050 316 Sample 2006 1376 321 Alkalinity P 230 156 330 23.0 321 14.0 M 138 58.0 156 9.5 167 21.0 Total 368 214 486 32.5 488 318 35.0 Solids Total 131 436 565 430 785 470 1.26E+5 Suspended 1.76 1.95 2.67 2.33 84.3 18.6 1.54E+5 Dissolved 129 434 562 428 701 451 - Carbon content Total 57.1 37.1 75.0 1.3 73.8 48.9 32.5 Organic 15.4 14.1 14.0 5.5 15.9 13.0 28.5 Inorganic 41.7 23.0 61.0 - 57.9 45.9 4.0 Metals Calcium 3.4 2.8 7.4 0.2 68.0 16.4 42.0 Magnesium 1.1 0.7 0.5 0.3 6.3 1.8 7.0 . Sodium 252 164 280 50.4 249 199 10.1 Iron 0.56 0.46 0.09 0.04 0.14 0.26 0.32 Inorganics Phosphates 0.07 0.05 0.05 0.05 0.05 0.05 0.05 Chlorides 31.4 0.2 17.0 3.2 8.1 12.0 2.8 Sulphates 110. 89.8 98.6 66.9 76.5 88.3 74.2 Silica 1.4 2.3 1-1 0.4 1.2 1.3 0.4 Units : pH = pH units Phosphates = mgofP/L Conductivity = |lS/cm @ 25 C Chlorides = mg of Cl /L Alkalinity = mg/L as CaC03 Sulphates = mg of S04/L Solids Silica = mg of Si02/L Carbon content — mg/L Metals 199 Condensate return Date of sample collection Parameter 3-May 8-May 10-May 15-May 17-May 24-May Avg. General p H 8.9 8.0 8.9 9.0 9.2 8.1 8.7 Conductivity 13.0 12.4 18.0 18.3 22.4 11.8 16.0 Alkal ini tv P 11 - 0.7 1.5 1.8 - M 4.4 4.0 4.0 4.3 4.5 4.8 Total 5.5 4.0 4.8 5.8 6.3 4.8 5.2 Solids Total 66.3 27.5 0.0 238.4 63.8 30.5 71.1 Suspended 0.17 0.00 0.00 0.40 0.63 0.00 0.20 Dissolved 66.1 27.5 0.0 238.0 63.1 30.5 70.9 Carbon content Total 5.8 5.7 4.2 0.0 8.4 5.6 5.0 Organic 4.3 4.3 3.2 4.3 4.2 4.2 4.1 Inorganic 1.5 1.4 1.0 - 4.2 1.4 1.9 Metals Calcium 0.4 0.3 0.3 0.3 0.1 0.2 0.2 Magnesium 0.3 0.2 0.1 0.2 0.1 0.1 0.2 Sodium 1.1 0.0 3.1 1.5 0.7 1.6 1.3 l ion 0.04 0.22 0.59 0.15 0.18 0.04 0.20 Inorganics Phosphates 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Chlorides 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Sulphates 2.1 1.9 1.7 1.0 1.9 1.0 1.6 Sil ica 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Units : p H = p H units Conductivity = | iS/cm @ 25 C Alkalinity = mg/L as C a C 0 3 Solids — Carbon content — mg/L Metals — Phosphates = mg of P / L Chlorides = mg of C l / L Sulphates = mg of S 0 4 / L Sil ica = mg of S i 0 2 / L 200 Boiler blowdown Date of sample collection Parameter 3-May 8-May 10-May 15-May 17-May 24-May Avg. General pH 11.4 11.5 11.6 11.5 11.6 11.4 11.5 Conductivity 2084 3853 4724 2666 3602 2799 3288 Alkalinity P 167 230 306 222 v 292 224 M 45.0 78.0 72.0 58.0 68.0 64.0 Total 212 308 378 280 360 288 304 Solids Total 1265 Suspended 4.29 Dissolved 1261 1910 2080 1558 19.6 43.9 1.18 1890 2036 1557 1702 1320 1639 0.30 18.5 14.6 1702 1301 1625 Carbon content Total 48.2 Organic 37.8 Inorganic 10.4 Metals Calcium 2.9 Magnesium 1.0 Sodium 358 Iron 0.95 77.8 93.4 44.2 57.6 60.9 37.6 20.2 32.5 6.6 1.2 2.0 0.1 1.0 1.2 0.4 603 676 417 1.08 5.55 0.08 73.8 63.5 66.8 46.6 44.5 47.5 27.2 19.0 19.3 0.1 1.0 1.2 0.2 0.7 0.8 503 397 492 0.17 0.48 1.39 Inorganics Phosphates 6.24 10.4 7.02 7.65 8.32 8.59 8.04 Chlorides 15.5 21.8 24.5 15.1 17.8 15.6 18.4 Sulphates 613 963 1134 656 756 579 783 Silica 5.5 6.7 8.0 7.2 8.6 6.5 7.1 Units : pH = pH units Conductivity = (iS/cm @ 25 C Alkalinity = mg/L as CaC03 Solids — Carbon content — mg/L Metals — Phosphates = mg of P/L Chlorides - mg of Cl/L Sulphates = mg of S04/L Silica = mg of Si02/L 201 Sulphur Plant blowdown Parameter 3-May Date of sample collection 8-May 10-May 15-May 17-May 24-May Avg. General pH 11.0 11.0 11.0 11.2 11.2 11.1 11.1 Conductivity 1120 1665 1451 1399 1466 1478 1430 Alkalinity P 94.5 106 105 128 127 122 M 34.5 35.0 36.0 38.0 39.0 40.0 Total 129 141 141 166 166 162 151 Solids Total 849 843 609 1013 764 679 793 Suspended 0.33 0.00 0.89 1.21 1.41 0.32 0.69 Dissolved 848 843 608 1011 762 678 792 Carbon content Total 40.5 48.9 49.3 40.7 46.3 48.5 45.7 Organic 33.0 36.3 32.9 35.2 35.1 34.5 34.5 Inorganic 7.5 12.6 16.4 5:5 11.2 14.0 11.2 Metals Calcium 1.3 0.3 0.3 0.3 0.3 0.2 0.4 Magnesium 0.5 0.4 0.3 0.4 0.4 0.5 0.4 Sodium 207 241 223 234 218 194 219 Iron 0.31 0.25 0.68 0.23 0.17 0.07 0.29 Inorganics Phosphates 4.88 5.47 4.95 6.52 6.57 7.09 5.91 Chlorides 8.8 8.7 8.3 9.6 8.9 8.2 8.8 Sulphates 360 441 418 362 355 276 369 Silica 3.1 3.4 3.4 4.0 3.5 3.7 3.5 Units : pH = pH units Conductivity = (iS/cm @ 25 C Alkalinity = mg/L as CaC03 Solids — Carbon content — mg/L Metals — Phosphates = mg of P/L Chlorides = mg of Cl/L Sulphates = mg of S04/L Silica = mg of Si02/L 202 Lime Pond discharge Parameter 3-May Date of sample collection 8-May 10-May 15-May 17-May 24-May Avg. General pH 9.6 9.9 9.9 10.1 10.4 10.4 10.0 Conductivity 4256 431 5327 4652 4478 5543 4114 Alkalinity P 21.8 33.0 27.5 35.5 36.0 46.0 M 45.5 50.0 33.0 41.0 30.0 35.5 Total 67.3 83.0 60.5 76.5 66.0 81.5 72.5 Solids Total 2663 2205 2515 2896 2343 2739 2560 Suspended 2.44 4.67 12.5 2.65 11.4 7.84 6.91 Dissolved 2660 2200 2503 2894 2331 2731 2553 Carbon content Total 24.9 31.8 26.5 20.4 25.7 30.7 26.7 Organic 13.7 15.7 15.2 15.2 18.2 19.4 16.2 Inorganic 11.2 16.1 11.3 5.2 7.5 11.3 10.4 Metals Calcium 260 159 261 241 198 207 221 Magnesium 22.2 17.5 19.5 26.5 17.8 15.8 19.9 Sodium 622 570 672 639 568 683 626 Iron 0.17 0.16 0.40 0.04 0.20 0.04 0.17 Inorganics Phosphates 0.16 0.24 0.05 0.05 0.05 0.05 0.10 Chlorides 918 682 914 1034 898 1017 911 Sulphates 792 615 601 578 579 550 619 Silica 4.3 4.5 4.4 3.5 3.0 ' 2.8 3.8 Units : pH = pH units Conductivity = |J.S/cm @ 25 C Alkalinity = mg/L as CaC03 Solids — Carbon content — mg/L Metals — Phosphates = mg of P/L Chlorides = mg of Cl/L Sulphates = mg of S04/L Silica = mg of Si02/L 203 Effluent Plant discharge Date of sample collection Parameter 3-May 8-May 10-May 15-May 17-May 24-May Avg. General pH 7.4 7.9 7.8 7.7 7.5 6.0 7.4 Conductivity 3316 4456 4390 3999 4513 4694 4228 Alkalinity P - - - - M 121 274 249 241 161 23.0 Total 121 274 249 241 161 23.0 178 Solids Total 2003 2849 2828 3280 3009 3201 2862 Suspended 14.9 6.15 8.55 5.96 6.44 24.7 11.1 Dissolved 1988 2843 2819 3274 3002 3177 2850 Carbon content Total 197 Organic 156 Inorganic 41.3 Metals Calcium 56.6 Magnesium 17.5 Sodium 499 Iron 3.14 220 212 192 131 128 123 89.1 84.5 69.7 53.4 54.4 54.9 16.8 16.7 17.1 596 599 580 3.11 3.31 3.28 182 209 202 129 192 143 53.0 17.0 59.1 53.4 62.7 55.9 16.8 18.0 17.2 561 516 558 3.42 4.88 3.52 Inorganics Phosphates 0.69 0.05 0.05 0.05 0.05 0.05 0.16 Chlorides 209 194 187 217 199 211 203 Sulphates 323 309 340 326 326 326 325 Silica 7.3 6.9 7.5 7.2 6.6 5.8 6.9 Units : pH = pH units Conductivity = |iS/cm @ 25 C Alkalinity = mg/L as CaC03 Solids — Carbon content — mg/L Metals — Phosphates = mg of P/L Chlorides = mg of Cl/L Sulphates = mg of S04/L Silica = mg of Si02/L 204 Polishing Pond discharge Date of sample collection Parameter 3-May 8-May 10-May 15-May 17-May 24-May Avg. General pH 7.3 7.8 7.9 7.8 7.6 7.1 7.6 Conductivity 3846 4471 4519 4341 4868 4985 4505 Alkalinity P M 73.0 119 125 119 116 51.0 Total 73.0 119 125 119 116 51.0 101 Solids Total 2655 2585 2480 3074 2919 2914 2771 Suspended 18.0 10.3 33.0 41.7 12.2 47.1 27.1 Dissolved 2637 2575 2447 3032 2907 2867 2744 Carbon content Total 95.6 Organic 73.7 Inorganic 21.9 Metals Calcium 146 Magnesium 21.7 Sodium 567 Iron 1.89 105 107 90.6 74.7 69.3 61.3 30.7 37.3 29.3 134 137 157 19.9 19.0 22.2 578 580 604 1.66 1.68 1.51 93.3 94.8 97.7 59.2 75.5 69.0 34.1 19.3 28.8 157 146 146 21.5 19.1 20.6 596 578 584 1.48 1.98 1.70 Inorganics Phosphates 0.51 0.47 0.35 0.11 0.11 0.06 0.27 Chlorides 606 ? 538 703 686 602 627 Sulfates 539 515 526 558 574 546 543 Silica 5.2 5.5 5.8 5.4 5.2 4.4 5.2 Units : pH = pH units Conductivity = |iS/cm @ 25 C Alkalinity = mg/L as CaC03 Solids — Carbon content — mg/L Metals — Phosphates = mg of P/L Chlorides = mg of Cl/L Sulphates = mg of S04/L Silica = mg of Si02/L 205 Flared water Date of sample collection Parameter 3-May 8-May 10-May 15-May 17-May 24-May Avg. General pH 6.0 5.4 5.4 5.2 4.8 No 5.4 Conductivity 60.2 Not measured Sample 60.2 Alkalinitv P i M 3.9 1.5 1.8 1.8 1.8 Total 3.9 1.5 1.8 1.8 1.8 2.1 Solids Total 125 12.5 ? 301 22.8 115 Suspended 8.75 0.00 7.31 • 58.3 1.68 68.8 Dissolved 116 12.5 llllllllll . 243 21.1 98 Carbon content Total 94.0 1481 433 187 205 700 Organic 97.7 1255 330 91.5 211 559 Inorganic llllillli 226 103 95.5 iiiiiiiiii 142 Metals Calcium No 0.3 0.2 2.8 0.1 0.9 Magnesium Sample 0.1 0.1 0.3 0.1 0.1 Sodium 0.9 0.1 4.6 0.6 1.5 Iron 1.93 2.05 7.14 4.51 3.91 Inorganics Phosphates 0.05 0.05 0.05 0.05 0.05 0.05 Chlorides 3.2 1.9 0.8 1.2 1.8 1.8 Sulphates 4.1 3.8 6.4 5.6 2.0 4.4 Silica 0.7 0.6 0.4 17.2 1.8 4.1 Units : pH = pH units Conductivity = |iS/cm @ 25 C Alkalinity = mg/L as CaC03 Solids — Carbon content — mg/L Metals — Phosphates = mg of P/L Chlorides = mg of Cl/L Sulphates = mg of S04/L Silica = mg of Si02/L I = dropped samples 206 APPENDIX D MASS BALANCE EQUATIONS AND ASSUMPTIONS 207 Treater System: The following streams were used in the mass balance: Incoming Outgoing -Raw water header -Treater water -Fresh brine solution -#3 Hot Lime Treater blowdown -8 psi steam -Spent regeneration brine -Vented steam The fresh brine solution was never sampled. It was assumed to be identical in chemical composition to the treated water, except for sodium and chloride levels. These values were calculated independently from figures given in the Water Treatment Manual: Use 7921b. of N a C l & 10480 USgal of water to regenerate 1 softener Concentration of: N a C l = (792 lb x 0.4536 lb/kg x 1 000 000 mg/kg)/(10480 USgal x 3.7854 L/gal) = 9055.8 mg/L Na = [NaCl] x 23/58.45 = 3563 mg/L C l = [NaCl] - [Na] = 5492 mg/L The 8 psi steam entering the system and the vented vapour leaving it were assumed to be identical not only to one another, but also to the condensate sampled elsewhere in the F N G P (see Appendix C). Boiler System The following streams were used in the mass balance: Incoming Outgoing -Boiler feedwater -450 psi steam -Boiler blowdown Chemical characteristics of the boiler feedwater (BFW) were derived from the treated water and condensate return flows, which mix in the deaerators prior to entry into the boilers. A sample calculation is shown below: 208 Total solids in B F W : = ((ConcentrationyyY x Flow-i-yy) + (Concentra t ion C o n d x F l o w G o n d ) ) / (Flowxw + F l o w C o n d ) The 450 psi steam leaving the boilers was assumed to have the same chemistry as the condensate return samples collected elsewhere in the F N G P . The flow of boiler feedwater into the boilers was assumed to be = to the flow of 450 psi steam and blowdown exiting the boiler. Lime Pond The following streams were used in the mass balance: Incoming Outgoing -#3 Hot lime treater blowdown -Lime pond discharge -Boiler blowdown -Softener regeneration blowdown -Sulphur plant blowdown Water samples were collected from each of these streams, so it was simply a case of multiplying know concentrations by the respective flow rates. Composite Discharge: The following streams were used in the mass balance: Incoming Outgoing -Effluent plant discharge -Polishing pond discharge -Lime pond discharge Water samples were collected from each of these streams, so it was simply a case of multiplying know concentrations by the respective flow rates. ESTIMATED HOT LIME TREATER AND ION-EXCHANGER BLOWDOWN CHARACTERISTICS Hot Lime Treater Blowdown: The water treatment manual stipulates that the hot lime tteater removes calcium, magnesium, silica and carbonate. It also indicates that if the total hardness of the inlet water is larger than the inlet M alkalinity, the lime treater effluent wi l l have the following characteristics: CO3 = 25 mg/L as CaC03 209 O H = 5 mg/L as CaC03 Total alk. = 30 mg/L as CaC03 M g =5 mg/L as C a C 0 3 Ca = (raw water hardness - hardness reduction) - final [Mg], where hardness reduction = alkalinity reduction Given that the inlet and outlet waters from the front-end softening system were observed to contain: Influent Outlet F low (m3/day) 1030 975 Ca (mg/L) 67.8 1.4 M g (mg/L) 15.3 0.5 Fe (mg/L) 0.4 0.6 SO4 (mg/L) 72.7 81.9 S i 0 2 (mg/L) 4.4 0.9 P 0 4 (mg/L) 0.06 0.07 Q (mg/L) 2.4 2.4 N a (mg/L) 10.6 50.5 D O C (mg/L) 8.4 6.1 p H 8.1 9.9 M . A l k (mg/L as CaC03) 133 18.4 T . A l k (mg/L as CaC03) 133 27.8 CO3 (mol/L) 1.6 x 10-5 1.0 x 10-4 C T (mol/L) 3.1 x 10-3 3.7 x 10-5 Product water from the hot lime treater should have contained: - hardness - alk. reduction - [Mg] - 5 mg/L as CaC03 = 1.2 mg/L - assumed to be identical to the outlet water - assumed to be identical to the oudet water - assumed to be identical to the outlet water - assumed to be identical to the outlet water - assumed to be identical to the outlet water - assumed to be identical to the [Na] observed in the single blowdown sample D O C =6.1 mg/L - assumed to be identical to the outlet water Ca = 42.5 mg/L M g = 1.2 mg/L Fe = 0.6 mg/L SO4 = 81.9 mg/L S i 0 2 = 0.9 mg/L PO4 = 0.07 mg/L C l = 2.4 mg/L N a = 10.1 mg/L 210 pH = 10.0 - [OH] of 5 mg/L as CaC03 = pH of 10.0 T. alk. = 30 mg/L CaC03 - as stipulated by water treatment manual CO3 = 1.2 x 10-4 mol/L - 25 mg/L as CaC03 = 1.2 x 10-4 mol/L C j =3.8X10-4 mol/L - calculated from total alkalinity and pH And the blowdown stream which flowed at 16.3 m3/day, would have had the following characteristics: Ca = 1640 mg/L - (1030 m3/day x 67.8 mg/L - 42.5 mg/L x 1014 m3/day) Mg = 887 mg/L - (1030 m3/day x 15.3 mg/L - 1.2 mg/L x 1014 m3/day) Fe = 0.3 mg/L - observed [ ] in single blowdown sample S0 4 = 74.2 mg/L - observed [ ] in single blowdown sample Si0 2 = 219 mg/L - (1030 m3/day x 4.4 mg/L - 1014 m 3/day x.0.9 mg/L) P0 4 = 0.05 mg/L - observed [ ] in single blowdown sample Cl = 2.8 mg/L - observed [ ] in single blowdown sample Na = 10.1 mg/L - observed [ ] in single blowdown sample DOC = 28.5 mg/L - (1030 m3/day x 8.4 mg/L -1014 m3/day x 6.1 mg/L) pH = 10.0 - assumed to be the same as the lime treater effluent C T = 1.7 x 10-1 mol/L - (1030 m3/day x 3.1 x 10-3 mol/L - 1014 m 3/day x 3.8 x 10-4 mol/L) C0 3 = 1.7 x 10-1 mol/L - [H 2C0 3] + [HC03] « < [C0 3], so [C T] = [CO3] Ion-exchange blowdown: Given the following data: Lime treater effluent Outlet water Flow (m3/day) 1014 975 Ca (mg/L) 42.5 1.4 Mg(mg/L) 1.2 0.5 Fe (mg/L) 0.6 0.6 SO4 (mg/L) 81.9 81.9 Si0 2 (mg/L) 0.9 0.9 P04(mg/L) 0.07 0.07 Cl (mg/L) 2.4 2.4 Na (mg/L) 10.1 50.5 DOC (mg/L) 6.1 6.1 pH(mg/L) 10.0 10.1 T.Alk (mg/L as CaC03) 30 27.8 211 C 0 3 (mol/L) C T (mol/L) 1.2 x 10-4 3.8 x 10-4 1.0 x 10-4 3.7 x 10-4 A n d that the brine used to regenerate the ion-exchangers consisted of 792 lbs of N a C l dissolved in 10480 USgal of treated/outlet water. The ion-exchanger blowdown should have had die following characteristics: Ca = 1070 mg/L M g = 19.9 mg/L Fe = 0.6 mg/L S 0 4 =81.9 mg/L S i 0 2 = 0.9 mg/L PO4 = 0.07 mg/L C l = 5490 mg/L N a =2331 mg/L D O C =6.1 mg/L p H = 11.0 T. alk. =318 mg/L CaC03 CO3 = 2.4 x 10-3 mol/L C T = 2.9 x 10-3 mol/L - (1014 m3/day x 42.5 mg/L - 975 m3/day x 1.4 mg/L) - (1014 m3/day x 1.2 mg/L - 975 m3/day x 0.5 mg/L) - assumed to be identical to the oudet water - assumed to be identical to the oudet water - assumed to be identical to the outlet water - assumed to be identical to the outlet water - [Cl] in brine used to regenerate the ion-exchangers - [Na] in brine used to regenerate the ion-exchanger + 2 x (equivalent mass of calcium magnesium removed by the ion-exchangers) - assumed to be identical to the outiet water - average value from 5 blowdown samples - average value from 5 blowdown samples - calculated from pH and total alkalinity readings - calculated from p H and total alkalinity readings. 212 APPENDIX E EQUATIONS USED IN THE COMPUTER SIMULATOR 213 S a (15 G H fa fa Q < fa fa G O fa Of! fa > O fa H C O C O C- fa H < <+H o e cu JS •4-» c o d C cd Hi X cu T3 3 "c3 > C _o cd a Vi SO c/5 on CD c/i H D OH + ON co CU Vi lH CU > Q cu D- + , ON + CO ON U co + Q NO + ON CO U + NO + r- X + CO r - CN Vi _ cu Q P N *H PH <L> cu -S •C C H 3 c C O Q % s i O 3 g^cs bp Q £ § ON CO a l l s § * > 3 « »| o -H P >~> S ̂  aa NO + NO "o 5 ll 53 ON + W C O CN r-H w r "NO" CD r—I ~ Q Vi i O /~- s r ° i ^ 3 r5 0 S c * ° + vi a co S-3 t CU ^ CN C > cu NO « rO i C O . / - N CU D , cU X! 3 cji vi O c Vi Cd ^ f j - b -5 H § ^ O 'I 3 _ •d n" 8 c3 u w U X « cj -° o c« + -y <u ^ c y ?? _ CD CU 3 3 oo r t ' 3 5 fa 3 o I i i O CO HC II O cd CL rH o o cj o ri P H CJ fa T3 J ; S > bfiCN S .a II 5 c y O U CU cd CU -s a CU CU Vi CU ox) o o ^ c 3 & « r 2 0 ^ S3 O j O ° TH CD V2 5 + 23 rS - 5 rS <» • rH g <D on •~- CU C <+H o Vi + Vi cd cd c« O •~ CU cd cd C g l ^1 r - T O r g S So, (D « 5 S.2 cd • > Jm o T3 C CD i ^1 o cd X ) cd bfl C • rH 3 CU < o 1—I * Tt * CN U i < o CN U l < o < o cd T3 "cd a •a o CU 13 > co O u I C O 0 u CN X X a. 1 o + X D H I o IS ^ CN U I < O i—i +" o o § 8 OO r - H CN NO <=> o * o ^ W ' I ( II 2 8 a. 0 0 i t— O N O O N - O ^ + x ?r 8 ? 0 O cd S O 3 < o < o * Tt * CN CN U l < o < o co 0 o 1 m o u CN X x + X a. o 2 8 " r̂ NO O CN o CH^ < 0 tH O r2 CO O 3 S O cf O CN u < o r—I o o o o o o o IT) r-H CN CN U <1 D . 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Tn C D o u ffi ffi OH o rH 0 0 r - U <D 3 C N * •a N O C D o X bX) 3 O ft X >D o oo 13 O oo cd oo 3 O • r H cd 3 cr CD oo cd X ) CD a cd C O vo CD ffi X Ml 3 O ft X » *n ffi OO 13 CD 00 cd 00 3 _o ea 3 cr <D oo cd X> CD a cd C O o II o C N r ^ X be 3 O oo =3 <D CD oo cd 00 3 O •n cd 3 CD 3 CD cd X) CD a cd C O 0 0 wi O +H T J ID In (D _o oo cd 3 ffi D H HH cd ? i T J CD .CD ft <D X oo 8 U", T J • 2 vo & C N c/o (D U oo C N fc o C D fc C N "ct C D C D fc fc H CD CD o o u u ffi C D o u C N H ffi U V O C D O CU ca cu ft CU CL. N O C D O H I U", CU H H ca ft H H C CU cu C o U V O C D fc U") 00 r H H H '3 3 O <X C N ft O r H on c 'oo 3 >> 3 TJ O CU <HH CU 1 to V O C D O 1 u-. ft CU H H ea fe H H CU 3 T3 © ft 0- V O C D D H U l CU H H ea ft c CD CU S o U o C N a 1 r- a cu CU X U CN O ffi •H3 O ea w .ti w> CU 1 £ o C O * o co V O C N s CU C<0 3 •-̂  TJ ea ffi o. 264 + . t l 3 2d CD ^ Cd r> i—1 3 cf> S K 8 c o o H td w s co Q < tf cu co co U CQ Q Z < o cc o <u S H 4 = H-» c _o '4-1 a s -2 3 X CD T3 c cd cn C D 3 3 > cn C 0 • r-( -t-> a 3 0 1 PLl C D u H P CN H P w H co >< CO O CC CD CD • T t cn UO vo 3 CN tf tf tf CN co tf 0 0 CN tf + 00 OH g J 3 O bO JO o o S H £ 3 3 5 « o U h co O U CN DC • co O U tn CD t n C D U O cd 3 <D C D §•§ S o 83 tf 0 § < * T ? * <D =3 * fa • H cn CD H J T t co H • uo 3 CN O OB P T t co p I U O CD "u CQ ca u CD o T t C O p I uo cn 3 3 CD C D s 3 cn So cn o tf CD 4 3 0 . I H C+H C D 3 •1—I 3 1 C D tf o < CC H Z W u z o u w z r-> tf CQ CN VO Q CO T t Q CD ca •a CD CD fa c# O -4-» cd OH C D M 3 JO s" O •a _cd On 3 cd 3 C D O H O C D JO cd • T H =3 > T t ca CD j> O CD CD CD vo CO o O cn C D C D 3 3 I H H2 cd cn 3 O *H-> cd & C D 3 c3 CN V O w co T t w CD H ^ ea CD 3 •O o u tf V O C O Da 1 ^ — i DC v—H C D C D 3 3 tf tf I H cd cn 3 O *-*-> cd E r C D S3' 3 3 e CN V O PH CO 2 ca CD CD c o U CN VO PH I CO uo PH C D O S H B cd fa 3 C D C D 3 O C D C D 3 •c <+H 3 C D O 3 O C D CN VO HH CO T t DC tf W •> tf Q tf tf s- CD H H ca •o CD CD COl H H 265 o CJ H ti ti ffi co Q «< cu co co U C Q Q Z o X o (U •~ CD X •*-> C _o ' - * H cd 3 i n 3 i x CD T J 3 cd oo CD _3 I d > 00 C _o cd 3 0 1 m CD u in -i—» > 1 cd s cn cd ^t X CD CD cd - * H c o ft o CD H H ^ cl C H II 2 2 C CD O cd I .CD O CS s cd CD oo HH (D > fi O CD X O fe V O r—> o ca m X c r - i o 00 •a 3H cd CD o CD c H H CD o nc  s o fi CD 00 o VO cn ^ CN ^rt > vo ^-j H , ^ t 00 bO <D C H H . H H cd > . H H CD CD CD fi ^ T3 CD O *-> DH . S U IS S 9 • f t fV> 00 •ft C >,'ft X DH cd H O s CD oo 00 cd ti H CO CO Z O HH H «! S < ti U ti c- X ti H ft 2 CD cd cd o O0 II 3 . 5 3 • f t DH ffi DH H-» cd fe ft CD 3 T3 O ft DH 3 <D -3 HH OO 3 cd CD e ft <D X H - » o CD £ o oo X> H H Is O H DH 00 ft 2 cd fe H H CD 3 CD T J C O • f t ft £ fi< w c co 2 U 5 CQ c ĉ  "f i , cd , H f t ft & T j 1 c/3 2 fi c CD CD C o CD o cd (D DH o cd CD H H o ffi OH Tt m H J ffi a ft CU H H CS fe H-̂ CD 3 "O O ft CU >n cn •rt z CN V O Z + cn "̂ t in >n Z Z i in T t Z o V D z V O •n Z c CD C/3 3 T3 C3 ffi a. ft H H « fe H H 8 fe T3 O QH H U + U o Q • cd u cn O U CN ffi I C O ffi P OH U .s u T J X I CD CD > .CD. O > c OH cn H H X ) B CD cn cn cd O Cd cd o cn <D o m IS O cD H H O S il 52 fi ?d aj > 3 fi ~ - 2 B •3 a •- oo V, ^ CD oo CO -ft U £ CQ CD" H H (D * H ft 3 CD 1 2 O H O cd T3 CD > O B 2 B 3 -CD CD H H cd x 3 & 3 O r: 2 s OH C3 ST Cd C H « fe X _ H CD T j X I CD CD •ft- 00 * ^ C H CD ^ o o o " f t H H O H ^ H H T D - 3 ft CD cd 3 " d s g rt § • i - ."2 cn -ft- CU >n Tt cu o V O cu vo -ct C U cu > oo O C3 E3 3 'I u 266 o OH C D o N O OH cd 3 o £ cd c o J O u CD o H 267 APPENDIX F SIMULATOR SUMMARY SHEETS 268 A summary sheet was made every time a different scenario was tested with the computer simulator. A s a result, more than 100 summary sheets were generated over the course of this study. While all of them are included on the computer disk accompanying this document, only a few were converted into hard copies and included in this appendix to illustrate the type of information that was inputted into the simulator. 269 ill(gfe°®01Ksl =©8®§]<i m© , ! © i s D ffU® LT@©̂ (gO@ Test Conditions Raw water origin: No name creek NF R.O. B/C Volume 8# vented: 0.0 m3/day # stages N/A 1 1 Softener type: lon-X Water temp (C) N/A 35 25 Water recycling: Removal -Brine disposal Evaporated monovalent N/A 9 6 % 99 .99% -Water recycled? no divalent N/A 9 8 % 99 .99% TOC N/A 9 0 % 99 .99% Water recovery: 9 0 % Nanofiltration Reverse Osmosis unit 1 unit 2 unit 3 unit 1 unit 2 unit 3 Water recovery N/A N/A N/A 5 0 % N/A N/A Brine recycle N/A N/A N/A Not avaifa ale •• Of rto U$e % recycle - N/A N/A Blending Of no use N/A % of product from #1+2 into #3 N/A Feedwater pH N/A N/A N/A 5.8 N/A N/A adjustment N / A N / A - 1.8 N / A N / A Feedwater Ca N/A Not important 60 Not important adjustment N / A Not available 53 Not avartabte Results Solubility Check Nanofiltration Reverse Osmosis unit 1 unit 2 unit 3 unit 1 unit 2 unit 3 CaSCM N/A N/A N/A ok N/A N/A CaC03 N/A N/A N/A ok N/A N/A MgC03 N/A N/A N/A ok N/A N/A Mg(OH)2 N/A N/A N/A ok N/A N/A Water flows F.E.T. inlet Lime blow. Soften blow. T.water R.O. inlet R.O. waste B/C feed m3/day 578.3 13.9 19.0 545.3 281.6 140.8 140.8 Water quality Raw Water from Treated Current Final waste water RO & B/C water T. water Solid Flow m3/day 407.4 267.5 545.3 - - Chern. Ca mg/L 81.3 1.3 1.4 1.4 3.2E+01 kg/day Mg mg/L 18.3 0.3 0.5 0.5 4.2E+00 kg/day Fe mg/L 0.39 0.0 0.6 0.6 4.2E-01 kg/day S 0 4 mg/L 86.8 7.4 61.6 81.9 9.6E+01 kg/day Si02 mg/L 5.2 0.1 0.9 0.9 1.2E+00 kg/day P04-P mg/L 0.06 0.01 0.07 0.07 9.1E-02 kg/day Cl mg/L 2.9 19.2 2.1 2.4 1.2E+02 kg/day Na mg/L 12.5 20.3 49.5 50.5 1.3E+02 kg/day DOC mg/L 9.3 8.4 6.0 6.1 2.0E+01 kg/day pH 7.9 4.7 10.0 10.1 C03 mol/L 1.4E-05 2.1E-06 1.4E-04 1.2E-04 7.6E-04 kg/day HC03 mol/L 3.6E-03 1.4E-03 3.0E-04 2.0E-04 7.2E+00 kg/day H2C03 mol/L 1.0E-04 1.0E-04 7.1E-08 3.7E-08 1.3E+00 kg/day Ctot mol/L • 3.7E-03 1.5E-03 4.4E-04 3.1E-04 Required pH adjustments: 2.8 for recyc. H20 pH=7.5 Total 414 .8 kg/day 270 H=@ficH§@ [R ©8 \0K, ir@(g^©l@ Test Conditions Raw water origin: No name creek NF R.O. B/C Volume 8# vented: 0.0 m3/day # stages N/A 1 1 Softener type: lon-X Water temp (C) N/A 35 100 Water recycling: Removal -Brine disposal Evaporated monovalent N/A 9 6 % 99 .99% -Water recycled? yes divalent N/A 9 8 % 99 .99% TOC N/A 9 0 % 99 .99% Water recovery: 9 0 % Nanofiltration Reverse Osmosis unit 1 unit 2 unit 3 . unit 1 unit 2 unit 3 Water recovery N/A N/A N/A 5 0 % N/A N/A Brine recycle - N/A N/A Not avaHa ale / Of OP U$e % recycle - N/A N/A Blending Of no use N/A % of product from #1+2 into #3 N/A Feedwater pH N/A N/A N/A 5.8 N/A N/A adjustment N / A N / A - 1.8 N / A N / A Feedwater Ca N/A Not tmportant 62 Not important adjustment N / A Not available 0 Not available Results Solubility Check Nanofiltration Reverse Osmosis unit 1 unit 2 unit 3 unit 1 unit 2 unit 3 CaS04 N/A N/A N/A ok N/A N/A CaC03 N/A N/A N/A ok N/A N/A MgC03 N/A N/A N/A ok N/A N/A Mg(OH)2 N/A N/A N/A ok N/A N/A Water flows F.E.T. inlet Lime blow. Soften blow. T.water R.O. inlet R.O. waste B/C feed m3/day 536.6 7.2 3.8 525.5 239.9 119.9 119.9 Water quality Raw Recycled Treated Current Final waste water Water water. T. water Solid Flow m3/day 137.8 227.9 525.5 - - Chern. Ca mg/L 81.3 1.3 1.4 1.4 1.4E+01 kg/day Mg mg/L 18.3 0.2 0.5 0.5 2.6E+00 kg/day Fe mg/L 0.39 0.0 0.3 0.6 3.9E-01 kg/day S 0 4 mg/L 86.8 5.8 25.3 81.9 6.4E+01 kg/day Si02 mg/L 5.2 0.1 0.9 0.9 8.8E-01 kg/day P04-P mg/L 0.06 0.01 0.04 0.07 9.0E-02 kg/day Cl mg/L 2.9 7.9 4.2 2.4 4.3E+01 kg/day Na mg/L 12.5 14.7 16.6 50.5 8.0E+01 kg/day DOC mg/L 9.3 9.7 6.0 6.1 2.0E+01 kg/day pH 7.9 7.5 10.0 10.1 C03 mol/L 1.4E-05 2.2E-06 7.0E-05 1.2E-04 7.8E-04 kg/day ; HC03 • mol/L 3.6E-03 1.5E-03 1.5E-04 2.0E-04 6.5E+00 kg/day H2C03 mol/L 1.0E-04 1.1E-04 3.5E-08 3.7E-08 1.2E+00 kg/day Ctot mol/L 3.7E-03 1.6E-03 2.2E-04 3.1E-04 Required pH adjustments: 2.8 for recyc. H20 pH=7.5 Total 233.7 kg/day 271 Test Conditions Raw water origin: No name creek NF RO. B/C Volume 8# vented: 0.0 m3/day # stages 3 1 1 Softener type: NF Water temp (C) 40 35 25 Water recycling: Removal -Brine disposal Evaporated monovalent 67% 9 6 % 99 .99% -Water recycled? no divalent 94% 9 8 % 99 .99% TOC 9 8 % 9 0 % 99 .99% Water recovery: 9 0 % Nanofiltration Reverse Osmosis unit 1 unit 2 unit 3 unit 1 unit 2 unit 3 Water recovery 7 5 % 5 0 % 7 5 % 5 0 % N/A N/A Brine recycle - no yes Not avallalal i? • 01 HP Use % recycle . . . -• 20% 1 00% Blending Of no use no % of product from #1+2 into #3 50% Feedwater pH 6.5 6.0 6.2 5.8 N/A N/A adjustment 2.7 0.8 - 1.8 N / A N / A Feedwater Ca 35.0 Not important 65 Not important adjustment 0.0 Not available 50 Not avaiJa|)fe : :: :: :: :: :: :x :: :: ::& Results Solubility Check Nanofiltration Reverse Osmosis unit 1 unit 2 unit 3 unit 1 unit 2 unit 3 CaS04 ok ok ok ok N/A N/A CaC03 ok ok ok ok N/A N/A MgC03 ok ok ok ok N/A N/A Mg(OH)2 ok ok ok ok N/A N/A Water flows F.E.T. inlet Lime blow. Soften blow. T.water R.O. inlet R.O. waste B/C fe m3/day 576.1 13.9 89.9 472.2 279.3 139.7 139. Water quality Raw RO + B/C Treated Current Final waste water Water water T. water Solid Flow m3/day 405.1 265.4 472.2 - • - Chern. Ca mg/L 81.3 1.38 0.28 1.4 3.2E+01 kg/day Mg mg/L 18.3 0.33 0.01 0.5 4.2E+00 kg/day Fe mg/L 0.39 0.03 0.00 0.6 4.3E-01 kg/day S 0 4 mg/L 86.8 7.67 0.50 81.9 9.9E+01 kg/day Si02 mg/L 5.2 0.09 0.01 0.9 1.2E+00 kg/day P04-P mg/L 0.06 0.01 0.00 0.07 9.0E-02 kg/day Cl mg/L 2.9 3.54 0.71 2.4 2.2E+01 kg/day Na mg/L 12.5 ' 10.81 3.15 50.5 6.9E+01 kg/day DOC mg/L 9.3 8.30 0.01 6.1 2.0E+01 kg/day PH 7.9 4.7 10.0 10.1 C03 mol/L 1.4E-05 2.1E-06 8.1E-05 1.2E-04 7.6E-04 kg/day HC03 mol/L 3.6E-03 1.4E-03 1.7E-04 2.0E-04 7.2E+00 kg/day H2C03 mol/L 1.0E-04 1.0E-04 4.0E-08 3.7E-08 1.3E+00 kg/day Ctot mol/L 3.7E-03 1.5E-03 2.5E-04 3.1E-04 Required pH adjustments: 2.8 for recyc. H20 pH=7.5 Total 256.3 kg/day 4.2 for T.W. from NF = 10.0 272 HJ®©te=©[rQĉ l wb@$®% = H=@{lca<p E©, BO®, IMF, ir@cĝ c@l® Test Conditions Raw water origin: No name creek NF R.O. B/C Volume 8# vented: 0.0 m3/day # stages 3 1 1 Softener type: NF Water temp (C) 40 35 25 Water recycling: Removal -Brine disposal Evaporated monovalent 67% 9 6 % 99 .99% -Water recycled? yes divalent 94% 9 8 % 99 .99% TOC 9 8 % 9 0 % 99 .99% Water recovery: 9 0 % Nanofiltration Reverse Osmosis unit 1 unit 2 unit 3 unit 1 unit 2 unit 3 Water recovery 7 5 % 7 5 % 7 5 % 5 0 % N/A N/A Brine recycle - no yes NiS 3le Of rto y$<j % recycle - 2 0 % 1 0 0 % Blending Of no use no % of product from #1+2 into #3 5 0 % Feedwater pH 6.5 6.0 6.2 5.8 N/A N/A adjustment 2.7 0.8 - 1.8 N / A N / A Feedwater Ca 6.0 Not important 68 Not important adjustment 0.0 Not available 0 Not availabie Results Solubility Check Nanofiltration Reverse Osmosis unit 1 unit 2 unit 3 unit 1 unit 2 unit 3 CaS04 ok ok ok ok N/A N/A CaC03 ok ok ok ok N/A N/A MgC03 ok ok ok ok N/A N/A Mg(OH)2 ok ok ok ok N/A N/A Water flows F.E.T. inlet Lime blow. Soften blow. T. water R.O. inlet R.O. waste m3/day 521.2 7.4 41.9 471.8 224.5 112.2 Water quality Flaw Recycled Treated Current Final waste water Water water T. water Solid Flow m3/day 137.0 213.3 471.8 - - B/C feed 112.2 Chern. Ca Mg Fe S 0 4 Si02 P04-P Cl Na DOC pH C03 HC03 H2C03 Ctot Req m g / L m g / L m g / L m g / L m g / L m g / L m g / L m g / L m g / L mo l /L mo l /L : mol /L mo l /L uired pH 81.3 18.3 0.39 86.8 5.2 0.06 2.9 12.5 9.3 7.9 1.4E-05 3.6E-03 1.0E-04 3.7E-03 adjustments: 1.43 0.26 0.04 6.34 0.09 0.01 4.43 13.36 10.23 7.5 2.4E-06 1.6E-03 1.2E-04 1.7E-03 2.8 4.2 0.04 0.01 0.00 0.19 0.01 0.00 0.82 2.88 0.01 10.0 6.2E-05 1.3E-04 3.1E-08 1.9E-04 1.4 0.5 0.6 81.9 0.9 0.07 2.4 50.5 6.1 10.1 1.2E-04 2.0E-04 3.7E-08 3.1E-04 1.4E+01 2.7E+00 4.0E-01 6.6E+01 8.9E-01 8.9E-02 2.3E+01 6.8E+01 2.0E+01 kg/day kg/day kg/day kg/day kg/day kg/day kg/day kg/day kg/day 6.7E-04 kg/day 6.6E+00 kg/day 1.2E + 00 kg/day for recyc. H20 pH=7.5 for T.W. from NF = 10.0 Total 202.6 kg/day 273 ESs](§fc=(i[n)d] mni©(a]@l = 11= Test Conditions Raw water origin: No name creek NF R.O. B/C Volume 8# vented: 0.0 m3/day # stages N/A 1 N/A Softener type: lon-X Water temp (C) N/A 35 N/A Water recycling: Removal -Brine disposal Deep well monovalent N/A 9 6 % N/A -Water recycled? no divalent N/A 9 8 % N/A TOC N/A 9 0 % N/A Water recovery: N/A Nanofiltration Reverse Osmosis unit 1 unit 2 unit 3 unit 1 unit 2 unit 3 Water recovery N/A N/A N/A 5 0 % N/A N/A Brine recycle N/A N/A N/A Not avatlable / Of rtO % recycle - N/A N/A Blending Ol no use N/A % of product from #1+2 into #3 N/A Feedwater pH N/A N/A N/A 5.8 N/A N/A adjustment N / A N / A - 1.8 N / A N / A Feedwater Ca N/A Not fmportant 65 Not important adjustment N/A Not av$ia&|$ 48 Not £v«iabte Results Solubility Check Nanofiltration Reverse Osmosis unit 1 unit 2 unit 3 unit 1 unit 2 unit 3 CaSC4 N/A N/A N/A ok N/A N/A CaC03 N/A N/A N/A ok N/A N/A MgC03 N/A N/A N/A ok N/A N/A Mg(OH)2 N/A N/A N/A ok N/A N/A Water flows F.E.T. inlet Lime blow. Soften blow. T.water R.O. inlet R.O. waste B/C fe m3/day 578.3 13.9 19.0 545.3 281.6 140.8 N/A Water quality Raw Recycled Treated Current Final waste water Water water T. water Liquid Solid Flow m3/day 407.4 0.0 545.3 - 140.8 - Chern. % of wastewater not recovered 50.0% Ca mg/L 81.3 0 1.4 1.4 2.2E+02 3.2E+01 kg/day Mg mg/L 18.3 0.0 0.5 0.5 3.0E+01 4.2E+00 kg/day Fe mg/L 0.39 0.0 0.6 0.6 3.0E+00 4.2E-01 kg/day S04 mg/L 86.8 0 61.6 81.9 6.8E+02 9.6E+01 kg/day Si02 mg/L 5.2 0.0 0.9 0.9 8.3E+00 1.2E+00 kg/day P04-P mg/L 0.06 0.00 0.07 0.07 6.5E-01 9.1E-02 kg/day Cl mg/L 2.9 0 2.1 2.4 8.7E+02 1.2E+02 kg/day Na mg/L 12.5 0 49.5 50.5 9.2E+02 1.3E+02 kg/day DOC mg/L 9.3 0.0 6.0 6.1 1.4E+02 2.0E+01 kg/day PH 7.9 0.0 10.0 10.1 6.1 C03 mol/L 1.4E-05 0.0E+00 1.4E-04 1.2E-04 5.5E-08 4.6E-04 kg/day HC03 mol/L 3.6E-03 0.0E+00 3.0E-04 2.0E-04 8.3E-04 7.2E+00 kg/day H2C03 mol/L 1.0E-04 0.0E+00 7.1E-08 3.7E-08 1.5E-03 1.3E+01 kg/day Ctot mol/L 3.7E-03 0.0E+00 4.4E-04 3.1E-04 2.3E-03 Required pH adjustments: 2.7 for recyc. H20 pH=7.5 Total 426.3 kg/day 274 LSii(gk=@[ni(a] TOdlcit] -H-sttag® m©, © W s 1 Test Conditions Raw water origin: No name creek NF R.O. B/C Volume 8# vented: 0.0 m3/day # stages N/A 1 N/A Softener type: lon-X Water temp (C) N/A 35 N/A Water recycling: Removal -Brine disposal Deep well monovalent N/A 9 6 % N/A -Water recycled? yes divalent N/A 9 8 % N/A TOC N/A 9 0 % N/A Water recovery: N/A Nanofiltration Reverse Osmosis unit 1 unit 2 unit 3 unit 1 unit 2 unit 3 Water recovery N/A N/A N/A 5 0 % N/A N/A Brine recycle N/A N/A N/A J : Of no u$<* % recycle - N/A N/A Blending Of no use N/A % of product from #1+2 into #3 N/A Feedwater pH N/A N/A N/A 5.8 , N/A N/A adjustment N / A N / A - 1.8 N / A N / A Feedwater Ca N/A Not important 75 Not important adjustment N / A Not available 1 1 Not avaa&bte Results Solubility Check Nanofiltration Reverse Osmosis unit 1 unit 2 unit 3 unit 1 unit 2 unit 3 CaS04 N/A N/A N/A ok N/A N/A CaC03 N/A N/A N/A ok N/A N/A MgC03 N/A N/A N/A ok N/A N/A Mg(OH)2 N/A N/A N/A ok N/A N/A Water flows F.E.T. inlet Lime blow. Soften blow. T.water R.O. inlet R.O. waste B/C feed m3/day 559.2 10.1 11.1 538.0 262.5 131.3 N/A Water quality Raw Recycled Treated Current Final waste water Water water T. water Liquid Solid Flow m3/day 257.1 131.3 538.0 - 131.3 - Chern. % of wastewater not recovered 50.0% Ca mg/L 81.3 3 1.4 1.4 1.7E+02 2.2E+01 kg/day Mg mg/L 18.3 0.5 0.5 0.5 2.6E+01 3.4E+00 kg/day Fe mg/L 0.39 0.1 0.4 0.6 3.1E+00 4.0E-01 kg/day S04 mg/L 86.8 1 2 43.3 81.9 6.1E+02 8.0E+01 kg/day Si02 mg/L 5.2 0.2 0.9 0.9 7.7E+00 1.0E+00 kg/day P04-P mg/L 0.06 0.01 0.05 0.07 6.9E-01 9.1E-02 kg/day Cl mg/L 2.9 26 7.5 2.4 6.3E+02 8.3E+01 kg/day Na mg/L 12.5 3 4 37.2 50.5 8.1E+02 1.1E+02 kg/day DOC mg/L 9.3 17.4 7.4 6.1 1.6E+02 2.1E+01 kg/day pH 7.9 7.5 10.0 10.1 6.1 C03 mol/L 1.4E-05 2.2E-06 1.4E-04 1.2E-04 5.6E-08 4.4E-04 kg/day HC03 mol/L 3.6E-03 1.4E-03 3.0E-04 2.0E-04 8.5E-04 6.8E+00 kg/day H2C03 mol/L 1.0E-04 1.1E-04 7.1E-08 3.7E-08 1.5E-03 1.2E+01 kg/day Ctot mol/L 3.7E-03 1.5E-03 4.4E-04 3.1E-04 2.3E-03 Required pH adjustments: 2.7 for recyc. H20 pH=7.5 Total 335.2 kg/day 275 , PW, ft W, ou® m©y©i® Test Conditions Raw water origin: No name creek NF R.O. B/C Volume 8# vented: 0.0 m3/day # stages 3 1 N/A Softener type: NF Water temp (C) 40 35 N/A Water recycling: Removal -Brine disposal Deep well monovalent 67% 9 6 % N/A -Water recycled? no divalent 94% 9 8 % N/A TOC 98% 9 0 % N/A Water recovery: N/A Nanofiltration Reverse Osmosis unit 1 unit 2 unit 3 unit 1 unit 2 unit 3 Water recovery 7 5 % 5 0 % 7 5 % 5 0 % N/A N/A Brine recycle - no yes Not available i Of fto uss % recycle - 2 0 % 1 0 0 % Blending Of no U&B no % of product from #1+2 into #3 5 0 % Feedwater pH 6.5 6.0 6.2 5.8 N/A N/A adjustment 2.7 0.8 - 1.8 N / A N / A Feedwater Ca 35.0 Not important 65 Not important adjustment 0.0 Not available 50 Net avaiJabte Results Solubility Check Nanofiltration Reverse Osmosis unit 1 unit 2 unit 3 unit 1 unit 2 unit 3 CaS04 ok ok ok ok N/A N/A CaC03 ok ok ok ok N/A N/A MgC03 ok ok ok ok N/A N/A Mg(OH)2 ok ok ok ok N/A N/A Water flows F.E.T. inlet Lime blow. Soften blow. T.water R.O. inlet R.O. waste B/C fe m3/day 576.1 13.9 89.9 472.2 279.3 139.7 N/A Water quality Raw Recycled Treated Current Final waste water Water water T. water Liquid Solid Flow m3/day 405.1 0.0 472.2 - 139.7 - Chern. % of wastewater not recovered 50 .0% Ca mg/L 81.3 0.00 0.3 1.4 2.3E+02 3.2E+01 kg/day Mg mg/L 18.3 0.00 0.0 0.5 3.0E+01 4.2E+00 kg/day Fe m g / L 0.39 0.00 0.0 0.6 3.1E+00 4.3E-01 kg/day S04 mg/L 86.8 0.00 0.5 81 .9 7.1E+02 9.9E+01 kg/day Si02 m g / L 5.2 0.00 0.0 0.9 8.3E+00 1.2E+00 kg/day P04-P mg/L 0.06 0.00 0.00 0.07 6.4E-01 9.0E-02 kg/day Cl mg/L 2.9 0.00 0.7 2.4 1.6E+02 2.2E+01 kg/day Na mg/L 12.5 0.00 3.2 50.5 4.9E+02 6.9E+01 kg/day DOC mg/L 9.3 0.00 0.0 6.1 1.4E+02 2.0E+01 kg/day pH 7.9 0.0 10.0 10.1 6.1 C03 mol/L 1.4E-05 0.0E+00 8.1E-05 1.2E-04 5.5E-08 4.6E-04 kg/day HC03 mol/L 3.6E-03 0.0E+00 1.7E-04 2.0E-04 8.4E-04 7.2E+00 kg/day H2C03 mol /L 1.0E-04 0.0E+00 4.0E-08 3.7E-08 1.5E-03 1.3E+01 kg/day Ctot mol/L 3.7E-03 0.0E+00 2.5E-04 3.1E-04 2.3E-03 Required pH adjustments: 2.7 for recyc. H20 pH=7.5 Total 267.8 kg/day 4.2 for T.W. from NF = 10.0 276 iSKS^®^ m©$®i ° H=ttiiKg® ^ ©, PW, Test Conditions Raw water origin: No name creek NF R.O. B/C Volume 8# vented: 0.0 m3/day # stages 3 1 N/A Softener type: NF Water temp (C) 40 35 N/A Water recycling: Removal -Brine disposal Deep well monovalent 67% 9 6 % N/A -Water recycled? yes divalent 94% 9 8 % N/A TOC 9 8 % 9 0 % N/A Water recovery: N/A Nanofiltration Reverse Osmosis unit 1 unit 2 unit 3 unit 1 unit 2 unit 3 Water recovery 7 5 % 65% 75% 5 0 % N/A N/A Brine recycle - no yes Nqt avaita ble .' Of no u$e % recycle - 2 0 % 100% Blending! Of no use no % of product from #1+2 into #3 5 0 % Feedwater pH 6.5 6.0 6.2 5.8 N/A N/A adjustment 2.7 0.8 1.8 N / A N / A Feedwater Ca 19.8 Not important 70 Not important adjustment 0.0 Not available 21 Nol awaiafete Results Solubility Check Nanofiltration Reverse Osmosis unit 1 unit 2 unit 3 unit 1 unit 2 unit 3 CaS04 ok ok ok ok N/A N/A CaC03 ok ok ok ok N/A N/A MgC03 ok ok ok ok N/A N/A Mg(OH)2 ok ok ok ok N/A N/A Water flows F.E.T. inlet Lime blow. Soften blow. T.water R.O. inlet R.O. waste B/C feed m3/day 542.8 10.1 60.4 472.2 246.1 123.0 N/A Water quality Raw Recycled Treated Current Final waste water Water water T. water Liquid Solid Flow m3/day 248.8 123.0 472.2 - 123.0 - Chern. % of wastewater not recovered 5 0 . 0 % Ca mg/L 81.3 2.80 0.15 1.4 1.8E+02 2.2E+01 kg/day Mg mg/L 18.3 0.55 0.01 0.5 2.7E+01 3.3E+00 kg/day Fe mg/L 0.39 0.07 0.00 0.6 3.4E+00 4.1E-01 kg/day S 0 4 rhg/L 86.8 13.47 0.33 81.9 6.6E+02 8.1E+01 kg/day Si02 mg/L 5.2 0.17 0.01 0.9 8.2E+00 1.0E+00 kg/day P04-P mg/L 0.06 0.01 0.00 0.07 7.3E-01 8.9E-02 kg/day Cl mg/L 2.9 7.77 1.02 2.4 1.9E+02 2.3E+01 kg/day Na mg/L 12.5 23.57 3.74 50.5 5.7E+02 7.0E+01 kg/day DOC mg/L 9.3 18.33 0.01 6.1 1.6E+02 2.0E+01 kg/day pH 7.9 7.5 10.0 10.1 6.1 C03 mol/L 1.4E-05 2.3E-06 7.9E-05 1.2E-04 5.9E-08 4.4E-04 kg/day HC03 mol/L 3.6E-03 1.5E-03 1.6E-04 2.0E-04 9.0E-04 6.8E+00 kg/day H2C03 mol/L 1.0E-04 1.1E-04 3.9E-08 3.7E-08 1.6E-03 1.2E+01 kg/day Ctot mol /L 3.7E-03 1.6E-03 2.4E-04 3.1E-04 2.5E-03 Required pH adjustments: 2.7 for recyc. H20 pH=7.5 Total 239.8 kg/day 4.2 for T.W. from NF = 10.0 277 APPENDIX G COST ESTIMATES 278 COST ESTIMATING FACTORS Reverse osmosis systems According to Osmonics, Inc. (located in Minnetonka, Minnesota), R O systems generally cost US$2 000 per gpm of produced permeate. Given their price estimate for a 360 m 3/day R O filter system (listed below), it was assumed that a dual-media filter in any R O assembly would account for 14.9 % of the total cost. The remaining 85.1 % would be involved in purchasing the R O membranes and associated support equipment. Equipment Price (US$) Dual-media filter 17 500 Chemical injection system 4 000 R O s k i d 80 000 Cleaning system 9 250 Membranes 7_5QQ Total H 8 250 Nanofiltration costs Nanofiltration system generally cost 85 % of the R O assemblies (Osmonics, Inc., personal com.). When no pretreatment equipment is required for the N F filters, as is the case when they are used in place of the ion-exchangers, they were assumed to cost 72.3 % of R O systems. BCS assembly B C S unit prices for three different flow rates were provided by Resources Conservation Company (located in Bellevue, Washington): Flow rate (m 3/dav) Cost (US$) 200 1 650 000 360 1 900 000 500 2 250 000 From a regression analysis on the three figures, B C S costs were estimated using the following equation: price = 1 990*feedwater flow + 1 230 235 279 Ion-exchangers Nalco Canada Inc. representative indicated that an ion-exchange unit would cost between $50 000 and $100 000 Canadian dollars, regardless of the particular ZED configuration. A price of $50 000 US dollars was used in the cost estimates. COST ESTIMATES Closed-Loop Designs 1-stage RO systems BE, BCS, IXa BE, BCS, NF a CD, BCS, IXa CD, BCS, NF a Flowb Cost Flowb Cost Flowb Cost Flowb Cost Equipment (m3/day) (US$) (m3/day) (US$) (m3/day) (US$) (m3/day) (US$) RO filters 120 37 453 112 35 049 269 83 992 257 80 245 RO pretreat: Ca removal - 50 000 - 50 000 - - - - Sand filter - 6 558 - 6 137 - - - - - BCS 120 1.47e6 112 1.45e6 269 1.77e6 257 1.74e6 NF filters - - 472 125 156 - - 478 126 906 Total 1.57e6 1.67e6 1.85e6 1.95e6 with initial flows 1.61e6 1.73e6 1.85e6 1.95e6 a BE = back-end, CD = composite discharge, IX = ion-exchange, NF = nanofilters, BCS = brine concentrator and spray dryer b flow = produced permeate for RO and NF, and feedwater for the BCS unit 280 2-stage RO models BE, BCS, IX a BE, BCS, NF a CD, BCS, IX a CD, BCS, NF a Flowb Cost Flowb Cost Flowb Cost Flowb Cost Equipment (m3/day) (US$) (m3/day) (US$) (m3/day) (US$) (m3/day) (US$) RO filters 146 45 711 135 42 171 397 123 880 . 382 119 196 RO pretreat: Ca removal - 50 000 - 50 000 - - - - Sand filter - 8 004 - 7 384 - - - - BCS 97.6 1.42e6 90.0 1.41e6 132 1.49e6 127 1.48e6 NF filters - - 472 125 262 - - 486 128 976 Total 1.53e6 1.63e6 1.62e6 1.73e6 with initial flows 1.57e6 1.69e6 1.77e6 1.87e6 a BE = back-end, CD = composite discharge, IX = ion-exchange, NF = nanofilters, BCS = brine concentrator and spray dryer b flow = produced permeate for RO and NF, and feedwater for the BCS unit BCS only configurations BE, BCS, IX a BE, BCS, NFa Flowb Cost Flowb Cost Equipment (m3/day) (US$) (m3/day) (US$) BCS 219 1.67e6 223 1.67e6 NF filters - - 471 125 050 Total 1.67e6 1.80e6 with initial flows 1.79e6 1.91e6 a BE = back-end, IX = ion-exchange, NF = nanofilters, BCS = brine concentrator and spray dryer b flow = produced permeate for NF, and feedwater for the BCS unit 281 Deep well configurations 1-stage RO options BE, IX a BE, NFa CD, IX a CD, NF a Flowb Cost Flowb Cost Flowb Cost Flowb Cost Equipment (m3/day) (US$) (m3/day) (US$) (m3/day) (US$) (m3/day) (US$) RO filters 131 40 981 123 38 421 514 160 474 490 152 871 RO pretreat: Ca removal 50 000 - 50 000 - - - - Sand filter 7 175 - 6 727 - - - - NF filters - 472 125 262 - - 480 127 331 Total 98 156 220 410 160 474 280 202 with initial flows - 101 660 226 500 161 582 281 257 a BE = back-end, CD = composite discharge, IX = ion-exchange, NF = nanofilters b flow = m3/day of produced permeate 2-stage RO designs BE, IX a BE, NFa CD, IX a CD, NF a Flowb Cost Flowb Cost Flowb Cost Flowb Cost Equipment (m3/day) (US$) (m3/day) (US$) (m3/day) (US$) (m3/day) (US$) RO filters 158 49 346 148 46 105 518 161 817 496 155 002 RO pretreat: Ca removal 50 000 - 50 000 - - - - Sand filter 8 640 - 8 072 - - - - NF filters - 472 125 262 - - 487 129 082 Total 107 986 229 439 161 817 284 084 with initial flows 111 992 236 770 164 287 286 099 a BE = back-end, CD = composite discharge, IX = ion-exchange, NF = nanofilters 282

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