Revision 1 December 2014 Demineralizers and Ion Exchangers Student Guide GENERAL DISTRIBUTION GENERAL DISTRIBUTION: Copyright © 2014 by the National Academy for Nuclear Training. Not for sale or for commercial use. This document may be used or reproduced by Academy members and participants. Not for public distribution, delivery to, or reproduction by any third party without the prior agreement of the Academy. All other rights reserved. NOTICE: This information was prepared in connection with work sponsored by the Institute of Nuclear Power Operations (INPO). Neither INPO, INPO members, INPO participants, nor any person acting on behalf of them (a) makes any warranty or representation, expressed or implied, with respect to the accuracy, completeness, or usefulness of the information contained in this document, or that the use of any information, apparatus, method, or process disclosed in this document may not infringe on privately owned rights, or (b) assumes any liabilities with respect to the use of, or for damages resulting from the use of any information, apparatus, method, or process disclosed in this document. ii Table of Contents INTRODUCTION ..................................................................................................................... 1 TLO 1 DEMINERALIZER OPERATION..................................................................................... 2 Overview .......................................................................................................................... 2 ELO 1.1 Demineralizers and Ion Exchangers Purpose .................................................... 3 ELO 1.2 Principles of Operation ..................................................................................... 4 ELO 1.3 Regeneration ..................................................................................................... 6 ELO 1.4 Changes in Demineralizer Operation .............................................................. 12 ELO 1.5 pH Effects on Demineralizer Use ................................................................... 15 ELO 1.6 Decontamination Factor .................................................................................. 17 ELO 1.7 Plant Evolutions that Affect Demineralizer Operation ................................... 20 ELO 1.8 Saturated Demineralizer .................................................................................. 22 DEMINERALIZERS AND ION EXCHANGERS SUMMARY ......................................................... 24 iii This page is intentionally blank. iv Demineralizers and Ion Exchangers Revision History Revision Date Version Number 0 Purpose for Revision New Document Performed By OGF Team Introduction This course will explore how demineralizers and ion exchangers maintain water quality and water chemistry during nuclear power plant operations. Water chemistry plays a vital role in nuclear power plant operations; it helps maintain radiation levels at minimums, controls reactivity poisons, and improves the durability of plant components through corrosion control. Rev 1 1 Demineralizers and ion exchangers equipment controls water chemistry in a plant. Proper water chemistry is important to safe plant operations because it minimizes corrosion products that could become activated and cause high radiation levels, and helps maintain level amounts of reactivity poisons in solution in a pressurized water reactor (PWR). Objectives At the completion of this training session, the trainee will demonstrate mastery of this topic by passing a written exam with a grade of 80 percent or higher on the following Terminal Learning Objective (TLO): 1. Explain demineralizer operation and its effect on power plant operation. TLO 1 Demineralizer Operation Overview Demineralizers and ion exchangers themselves are not mechanically complex; however, they do facilitate some complex chemical processes on a molecular level to manage the water qualities of various plant systems. Water quality and water chemistry are important because these factors provide short-term and long-term benefits and functions within various plant systems. Objectives Upon completion of this lesson, you will be able to do the following: 1. State the purpose of a demineralizer. 2. Describe the principles of demineralizer operation. 3. Describe the process of demineralizer regeneration. 4. Describe the following demineralizer conditions to include causes, hazards, and corrective measures as applicable: a. Excessive differential pressure b. Channeling c. Excessive temperature d. Breakthrough e. Leakage 5. Explain how demineralizer use affects pH. 6. Describe the decontamination factor and explain how it is calculated. 7. Describe plant evolutions that could affect demineralizer operation. 8. Explain the condition of a saturated demineralizer and the effect temperature has upon it. 2 Rev 1 ELO 1.1 Demineralizers and Ion Exchangers Purpose Introduction Demineralizers in nuclear power plants remove ionic impurities, filter or remove small particles, and help control pH of the water. Demineralizers are important for controlling water quality and chemistry because they provide short-term and long-term benefits and functions in the systems where they are included. Demineralizers and ion exchangers are passive components that have a major effect on system performance by maintaining the system chemistry stable and reducing the immediate effects of chemical excursions due to such events as condenser tube leaks and other heat exchanger tube leaks into clean systems. In the figure below, demineralizers provide filtration and ion exchange for all water going to the steam generators. Figure: Typical PWR Purpose Demineralizers (also called ion exchangers) hold ion exchange resins and transport water through the resins to filter and ionize the water. Ion exchangers are generally classified into two groups: single-bed ion exchangers (containing either an anion or a cation resin) and mixed-bed ion exchangers (containing both anion and cation resins). Key attributes of a demineralizer are as follows: Rev 1 3 ο· A demineralizer is a cylindrical tank with connections at the top for water inlet and resin addition, and connections at the bottom for the water outlet and resin removal. ο· Inside the demineralizer, there are upper and lower retention elements with a mesh size smaller than the resin beads that keep the resin beads within the demineralizer. ο· Water that needs purification enters the top at a set flow rate and flows down through the resin beads where the flow path causes a physical filter effect as well as a chemical ion exchange, resulting in purified water exiting the demineralizer. Knowledge Check Demineralizers are used in nuclear plants to… (select all that apply) A. remove ionic impurities. B. remove small particles. C. control the pH of water. D. remove oil impurities. ELO 1.2 Principles of Operation Ion Exchange Definition Ion exchange is an exchange of ions between two electrolytes or between an electrolyte solution and a complex solution. In most cases, the term denotes the processes of purification, separation, and decontamination of aqueous and other ion-containing solutions with solid polymeric resins. The process of ion exchange takes place within the demineralizer vessel. This process removes ionic impurities and replaces them with acceptable substitutes. Small resin beads serve as the vehicle to complete the ion exchange within the demineralizer. The resin beads shown in the figure below are porous and have many exchange sites for ion exchange to take place. The resin generally contains exchangeable ions that are harmless such as H+ or OH-. Figure: Resin Beads 4 Rev 1 There are different types of resin beads available; the specific application dictates the appropriate type of resin bead. Anion resins exchange ions with undesirable negative ions and typically use the OH- or hydroxyl ion. Cation resins exchange ions with undesirable positive ions and typically use the H3O+ or hydronium ion. Ion Exchange Reactions The reactions that take place within the ion exchanger are reversible and dependent on the resin selected. Numerous exchange reactions can take place; below are a few examples: π» + + ππ» − ↔ π»2 π π»2 π πππΆπ ↔ ππ+ + πΆπ − π − π» + + π + ππ» − + ππ+ + πΆπ − → π − ππ+ + π + πΆπ− + π» + ππ» − The R indicates the organic portion of the resin. The resins represented above are a hydrogen cation resin R-H+ and a hydroxyl anion resin R+OH-. The sodium chloride will separate from the water and form the Na+ and Clions. The hydrogen and hydroxyl ions from the resin react to form water. The anion resin will exchange the negative Cl- for the negative OH- ion. The cation resin will exchange the positive H+ for the positive Na+. These exchanges take place because the resin has a higher affinity for the undesirable ions than the mobile ions it contains. Ion affinity is selective and the resin will give up one of its ions in favor of one for which it has a higher affinity. Many elements serve as ion exchangers. The table below lists some common strong acid cation exchanger elements and compounds, as well as some strong base anion exchanger elements, and compounds. Selectivity of Ion Exchange Resins Strong Acid Cation Exchanger Strong Base Anion Exchanger Barium Iodide Lead Nitrate Calcium Bisulfite Nickel Chloride Cadmium Cyanide Copper Bicarbonate Zinc Hydroxide Magnesium Fluoride Potassium Sulfate Ammonia Rev 1 5 Strong Acid Cation Exchanger Strong Base Anion Exchanger Sodium Hydrogen Knowledge Check A demineralizer contains resin with the following properties: π − π» + + π + ππ»− What reactions would result if NaCl was in contact with the resin beads? A. π − ππ+ + π + πΆπ − + π» + ππ» − B. π − πΆπ− + π + ππ+ + π» + ππ» − C. π − π + + π» + πΆπ− + ππ + ππ» − D. π − ππ»− + π + π» + + πΆπ + ππ− Knowledge Check Anion resins contain _____________ ions while cation resins contain __________ ions. A. negative; positive B. positive; negative C. negative; hydroxyl D. hydronium; hydroxyl ELO 1.3 Regeneration Introduction Sustained operation will eventually exhaust the resin bed, as the ion exchanges deplete the exchangeable ions. Increased effluent conductivity is a common indication of resin bed exhaustion. The resin exchange sites no longer contain sufficient ions to exchange to be effective. Breakthrough describes that point when the impurities in the outlet or effluent of the demineralizer indicate resin exhaustion. A very small amount of impurities or unwanted ions will pass through the demineralizer during normal operation. Leakage refers to this small and often undetectable amount of unwanted ions. Larger amounts of leakage indicate breakthrough and 6 Rev 1 require regeneration of the resin bed for the bed to function at peak performance. Figure: Single-Bed Demineralizer Single-Bed Regeneration Regeneration of the resins in single-bed demineralizers usually occurs in place, without pumping the resins out to another location for regeneration. The regeneration process is the same for cation beds and anion beds. However, the regenerating solution is different. The table below lists the regeneration stages and describes the process in each stage. Stage What Happens Backwash Water is pumped into the bottom of the ion exchanger and up through the resin. This fluffs the resin and washes out any entrained particles. The backwash water goes out through the normal inlet distributor piping at the top of the tank, but the valves are set to direct the stream to a drain where the backwashed particles flow to a container for waste disposal. Regeneration Opening the dilution water valve dilutes concentrated acid or caustic to approximately 10 percent; a distribution system immediately above the resin bed introduces the dilute mix. The regenerating solution flows through the resin and out the bottom of the tank to the waste drain. Rinsing Rinsing removes any excess regenerating solution. Rinse water is pumped into the top of the tank, flows down through the resin bed, removes excess regenerating solution, and flows out the bottom drain. Rev 1 7 Stage What Happens Return to Service Once personnel close the drain valve and open the outlet valve, the ion exchanger is ready for service. Mixed-Bed Regeneration A mixed-bed demineralizer is a demineralizer that includes both cation and anion resin beads. In effect, it is equivalent to a number of single-bed demineralizers in series. In a mixed-bed demineralizer, hydrogen and hydroxyl ions replace more impurities and the effluent water is extremely pure. The conductivity of this water can often be less than 0.06 microsiemens per centimeter (μS/cm or μmho/cm). The design of mixed-bed demineralizers anticipates regeneration of the resin in place, but the regeneration process is more complicated than the regeneration of a single-bed ion exchanger. The table below lists the stages for mixed-bed regeneration and describes the process in each stage. Stage What Happens Backwash Backwash water enters the vessel at the bottom and exits through the top to a drain. The backwash water in a mixed-bed unit must also separate the resins into cation and anion beds in addition to washing out entrained particles. The anion resin has a lower specific gravity than the cation resin; therefore, as the water flows through the bed, the lighter anion resin beads float upward to the top. The mixed-bed becomes a split bed. The separation line between the anion bed at the top and the cation bed at the bottom is the resin interface. Some resins need to be depleted to be separated; other resins separate in either the depleted form or the regenerated form. Regeneration A mixture of dilution water and caustic solution flows into the top of the vessel, just above the anion bed. At the same time, a mixture of dilution water and acid enters the bottom of the vessel, below the cation bed. The flow rate of the caustic solution down to the resin interface is the same as the flow rate of the acid solution up to the resin interface. Piping removes both solutions at the interface and dumps them to a drain. During the regeneration step, it is important to maintain the cation and anion resins at their proper volume. If not done, the resin interface will not occur at the proper place in the vessel, exposing some resin to the wrong regenerating solution. 8 Rev 1 Stage What Happens Slow Rinse Flow of dilution water continues, with the caustic and acid supplies cut off. This two-direction rinse flushes out the last of the regenerating solutions from the two beds and into the interface drain. Rinsing from two directions at equal flow rates keeps the caustic solution from flowing down into cation resin and depleting it. Vent and Partial Drain The drain valve is opened, and some of the water is drained out of the demineralizer so that there will be space for the air that is needed to re-mix the resins. In the air mix step, a blower usually supplies pressurized air, which forces air in through the line entering the bottom of the ion exchanger. The air mixes the resin beads and then leaves through the vent in the top of the vessel. When the resin is mixed, slowly draining the water out of the interface drain while the air mix continues allows the resin to settle into position. Final Rinse The air is turned off and the vessel is refilled with water that is pumped in through the top. Running water through the vessel from top to bottom and out the drain rinses the resins, until a low conductivity reading indicates that the ion exchanger is ready to return to service. The following figure shows the regeneration process in its seven steps. Rev 1 9 Figure: Mixed-Bed Demineralizer Regeneration External Generation The design of some mixed-bed demineralizers calls for resin regeneration to occur externally, with the resins removed from the vessel, regenerated, and then replaced. The first step is to sluice the mixed bed with water (sometimes assisted by air pressure) to a cation tank. The resins are backwashed in this tank to remove suspended solids and to separate the resins. Sluicing removes the separated anion resins to an anion tank. Regeneration of the separated anion and cation resins uses the same techniques as single-bed ion exchangers. Sluicing moves the regenerated resins into a holding tank where air remixes them. Then, sluicing moves the mixed, regenerated resins back to the demineralizer. Typically, groups of condensate demineralizers use external regeneration, as having one central regeneration facility reduces the complexity and cost of installing several regenerators. External regeneration also allows keeping a 10 Rev 1 spare bed of resins in a holding tank. Then, when a demineralizer needs regeneration, it is out of service only for the time required to sluice out the depleted bed and sluice a fresh bed in from the holding tank. A central regeneration facility may also include an ultrasonic cleaner that can remove the tightly adhering coating of dirt or iron oxide that often forms on resin beads. This ultrasonic cleaning reduces the need for chemical regeneration. Knowledge Check When a mixed-bed demineralizer resin is exhausted, the resin should be replaced or regenerated because... A. ions previously removed by the resin will be released into solution. B. the resin will fracture and possibly escape through the retention screens. C. particles previously filtered out of solution will be released. D. the resin will physically bond together, thereby causing a flow blockage. Knowledge Check For a mixed-bed demineralizer, place the regeneration steps in order. Rev 1 A. Slow rinse B. Air mix C. Regeneration D. Rinse E. Backwash F. Vent and partial drain 11 ELO 1.4 Changes in Demineralizer Operation Demineralizer Operation Under normal operations, demineralizers and ion exchangers are a passive component that can either process a portion of or total system flow. There are no moving parts and therefore they are not subject to mechanical failures like a pump or motor, but there are For More internal components that can fail or deteriorate and affect Information performance. They are susceptible to effects of temperature, flow rate changes, and chemical saturation. This section will discuss the indications, effects, and causes for these conditions. Differential Pressure Instrumentation measures key demineralizer factors that operators monitor including flow rate, inlet pressure, outlet pressure, and differential pressure across a demineralizer. Personnel use these indications to identify offnormal operating conditions as well as help in preventing them. The differential pressure across the demineralizer is a valuable tool in assessing demineralizer operation. The demineralizer will act as a filter removing suspended solids that cannot pass through the resin and retention element. The more materials removed, the higher the resistance to flow or differential pressure. A lower than normal differential pressure could indicate the demineralizer is operating at a reduced capacity, whereas a high differential pressure could indicate clogging or a flow rate that is too high. ο· The differential pressure increases with many demineralizer problems such as resin overheating, crud/particulate buildup, and excessive flow rate. As the operating time increases, trapped suspended solids raise the differential pressure. Personnel should expect this differential increase. A higher than expected differential pressure could indicate a blockage in the demineralizer. ο· The particles trapped within the resin will lower the rate of ion exchange. Routine flushing of demineralizers will remove excess particulate that has accumulated. Excessive suspended particles can form a mat on the surface of the resin beads that may also lead to channeling. ο· It is important to control the flow through the demineralizer to prevent channeling of the resin. An increased conductivity on the demineralizer outlet may indicate channeling in the demineralizer. Lower than expected differential pressure could also indicate channeling through the resin bed. High Flow Rate and Channeling An abnormally high flow rate could cause several problems. Under normal conditions, the lower retention element holds the resin beads in the 12 Rev 1 demineralizer. A flow rate that exceeds the design rate could force the resin beads through the retention element. The organic resin material could break down into small resin fines (material that is not an intact resin bead), which will pass through the retention element. Resin within the system could cause problems with other components. High flow rates may result in a sudden increase in conductivity at demineralizer outlet. Under high flow rates, channels develop in the resin bed. Channeling of the resin will reduce not only the ion exchange that takes place, but also the mechanical filtration. The channel through the resin creates a preferential path of lower resistance for the fluid, indicated by a decrease in differential pressure and a probable increase in both ion concentration and conductivity in the outlet. If the flow rate is too excessive, the ion exchange may not have time to occur or not enough exchanges will take place. Excessive flow rate results in an increase in flow measured at the outlet of the demineralizer. Temperature The resin beads in a demineralizer resin bed are susceptible to damage at elevated temperatures. The exchange sites will begin to break down around 140°F. The high operating temperature of coolant would rapidly damage the resin beads, therefore proper procedures must be followed to ensure resin remains intact. Damaged resin will give off an odor that is similar to dead fish. Lowering the temperature of influent may increase the affinity for a particular ion such as boron. The lower the temperature, the more boron the resin will hold. If the temperature increases, the resin affinity changes and releases some boron. Leakage and Breakthrough Eventually, the resin bed will be exhausted and unable to function at peak performance; an increased effluent conductivity is a common indication. The resin exchange site will run out of enough mobile ions to exchange and will no longer be effective Breakthrough is the term used to describe when the impurities in the outlet or effluent of the demineralizer indicate resin exhaustion. Very small amounts of impurities or unwanted ions will pass through during normal operation. This small and often undetectable amount is termed leakage. Larger amounts of leakage indicate imminent breakthrough and require resin regeneration to maintain peak demineralizer performance. Knowledge Check A sudden increase in conductivity of water at the outlet of a demineralizer will result from... Rev 1 13 A. increased demineralizer flow rate. B. reduced demineralizer inlet temperature. C. reduced demineralizer inlet conductivity. D. increased demineralizer effluent pressure. Knowledge Check – NRC Bank A condensate demineralizer differential pressure (D/P) gauge indicates 4.0 psid at 50 percent flow rate. Over the next two days, plant power changes have caused condensate flow rate to vary between 25 percent and 100 percent. Which one of the following combinations of condensate flow rate and demineralizer D/P, observed during the power changes, indicates an increase in the accumulation of corrosion products in the demineralizer? A. 100 percent flow, 15.0 psid B. 75 percent flow, 9.0 psid C. 60 percent flow, 5.0 psid D. 25 percent flow, 2.0 psid Differential Pressure Problem Solution Note To solve this problem, we must apply the pump law that flow rate is proportional to the square root of the D/P. Therefore, you have to plug in the expected D/Ps for each flow rate and find out which one exceeds the expected D/P. At 60 percent flow, the D/P should be: 60 2 ( ) × 4 = 5.76 ππ ππ 50 At 100 percent flow, the D/P should be: 100 2 ( ) × 4 = 16 ππ ππ 50 At 25 percent flow, the D/P should be: 25 2 ( ) × 4 = 1 ππ ππ 50 At 75 percent flow, the D/P should be: 75 2 ( ) × 4 = 11.25 ππ ππ 50 Only 25 percent flow rate has a higher than expected D/P and therefore indicates there is accumulation of corrosion products. 14 Rev 1 Knowledge Check Which one of the following will cause a large pressure drop across a demineralizer that is in operation? A. Channeling of flow through the demineralizer B. Depletion and resultant swelling of resin beads C. Accumulation of suspended solids filtered by the resin beads D. Improper demineralizer venting after resin fill Knowledge Check A lower than expected differential pressure across a demineralizer is an indication of... A. depletion of the cation exchange resin. B. channeling through the resin bed. C. improper resin regeneration. D. excessive accumulation of suspended solids. ELO 1.5 pH Effects on Demineralizer Use Introduction The pH is the molar concentration of dissolved hydrogen ions and is a measure of how acidic or basic a solution is. Hydrogen ion (H+) activity coefficients cannot be measured experimentally, so they are based on theoretical calculations. The pH scale measures the acidity or alkalinity of a substance. It ranges from 0 to 14. A pH of 7 is neutral. A pH less than 7 is acidic, and a pH greater than 7 is basic. Each whole pH value below 7 is ten times more acidic than the next higher value. For example, a pH of 4 is ten times more acidic than a pH of 5 and 100 times (10 times 10) more acidic than a pH of 6. The same holds true for pH values above 7, each of which is ten times more alkaline—another way to say basic—than the next lower whole value. For example, a pH of 10 is ten times more alkaline than a pH of 9. The pH scale, shown in the figure below, is not an absolute scale; it is relative to a set of standard solutions whose pH values have been established by international agreement. Rev 1 15 Figure: pH Scale The ion exchange process results in the formation of H+ and OH- exchanged ions from resins. The more basic solutions will have an excess of OH- ions, while the acidic solutions will contain excess H3O+. However, in a mixedbed demineralizer containing both resins, the pH effect of one cancels the pH effect of the other. To counteract this, a different type of cation resin (lithium) is used. The mixed-bed resin is comprised of a lithium-based cation resin with the anion resin. The mobile Li+ given up does not counteract the OH-, thereby increasing the pH. It is possible to control the pH of the solution by the ion exchange. In order to bias the reaction to maintain an excess of OH- ions and maintain a basic pH, operating procedures call for saturating the lithium beds prior to placing the demineralizer in service. Upon placing the bed in service and diverting the effluent to a holding tank versus back to the reactor coolant system, saturation of the lithium beds results. Knowledge Check If distilled water has a pH measurement of 7, then a pH greater than 7 indicates a(n) _________ while pH less than 7 indicates a(n) __________. 16 A. base; acid B. acid; base C. excess hydronium ions; excess hydroxyl ions D. excess H3O+; excess OH- Rev 1 Knowledge Check A mixed-bed demineralizer contains resins that exchange positive ions for H+ ions and exchange negative ions for OH- ions. What is the effect on effluent pH? A. The H+ ions and the OH- ions cancel each other and result in a neutral pH. B. The H+ ions are dominant and decrease pH. C. The OH- ions are dominant and raise pH. D. The pH is not affected by either H+ or OH- ions. ELO 1.6 Decontamination Factor Introduction Personnel often use the demineralization factor (decontamination factor) as a guide for determining when a resin bed is exhausted. The decontamination factor is the inlet conductivity divided by the outlet conductivity. To determine the percentage of impurities removed, divide the amount of impurities (conductivity) removed by ion exchanger by the amount of impurities (conductivity) entering the ion exchanger. The decontamination factor is a measure of the ion exchange and filtration process effectiveness. To determine the factor, you will need to know the inlet and outlet conductivities. Determining Decontamination Factor What is the decontamination factor (DF) for an ion exchanger with condensate of 20 μmho/cm entering and 0.4 μmho/cm exiting? Step Action 1. The DF ratio is set up to compare the outlet of the resin bed to the inlet of the resin bed. 2. Insert values for inlet and outlet conductivity. 3. Determine the DF. Rev 1 Formula π·πΉ = π·πΉ = ππβπππ ππβπππ’π‘ 20 ππβπππ 0.4 ππβπππ’π‘ π·πΉ = 50 17 Determining Impurities Removed Another useful value in determining the effectiveness of a resin bed is to determine the percentage of impurities removed. Step Action Formula 1. Percent impurities removed ratio is set up to compare the outlet of the resin bed to the inlet of the resin bed. % ππππ’πππ‘π¦ πππππ£ππ ππβππππππ£ππ = × 100 ππβπππ 2. Insert values for inlet and outlet conductivity. In the numerator, determine the amount removed by subtracting the outlet from the inlet conductivity. 3. Determine the factor. 4. Multiply by 100. 5. Determine the percentage of impurities removed. % ππππ’πππ‘π¦ πππππ£ππ (20 − 0.4) ππβππππππ£ππ = × 100 20 ππβπππ % ππππ’πππ‘π¦ πππππ£ππ (19.6) ππβππππππ£ππ = × 100 20 ππβπππ % ππππ’πππ‘π¦ πππππ£ππ = 0.98 × 100 % ππππ’πππ‘π¦ πππππ£ππ = 98% To restore the resin bed’s ability to exchange ions, it is necessary to either replace or regenerate the resin. The regeneration of an ion exchanger resin strips away the impurities removed from the system during demineralizer operation. Chemicals reverse the chemical process causing a release of unwanted ions refreshing the resin bed for further use. 18 Rev 1 Demonstration A demineralizer has been in service for 60 days. When first placed in service, the decontamination factor was 200. Currently, the inlet and outlet conductivities are as follows: For More ο· 35 μmho/cm entering Information ο· 0.3 μmho/cm exiting What is the decontamination factor now, what percentage of impurities are removed, and would you recommend regeneration? ο· 35μmho/0.3μmho = 117 ο· DF = 117 ο· (35-0.3) μmho removed)/(35 μmho in) =0.99 x 100% ο· impurities removed = 99% The demineralizer is removing 99 percent of the inlet contaminants. Although the DF has decreased to about 55 percent of the original value, it is still effective at removing unwanted ions. The demineralizer should remain in service. Normally demineralizers are replaced or regenerated when the DF is 25 or less. Knowledge Check – NRC Bank Which one of the following is an indication of resin exhaustion in a demineralizer? A. An increase in suspended solids in the effluent B. A decrease in the flow rate through the demineralizer C. An increase in the conductivity of the effluent D. An increase in the differential pressure across the demineralizer Knowledge Check – NRC Bank The decontamination factor for ionic impurities of a demineralizer can be expressed as... Rev 1 A. inlet conductivity minus outlet conductivity. B. outlet conductivity minus inlet conductivity. C. inlet conductivity divided by outlet conductivity. D. outlet conductivity divided by inlet conductivity. 19 Knowledge Check To determine the demineralization factor for a demineralizer, the parameters that must be monitored are inlet and outlet… A. pH. B. conductivity. C. suspended solids. D. pressure. ELO 1.7 Plant Evolutions that Affect Demineralizer Operation System Interrelationship Since demineralizers and ion exchangers are a support system used to adjust the chemistry of various systems in a power plant, changing conditions of the systems they serve can affect them. For example, during plant heatup or cooldown, a coolant purification system's inlet temperature can vary greatly. This may change the suspended solids in the coolant system and in turn affect the performance of the resin bed. The temperature and flow of the processed water can also directly affect demineralizer resins. Crud Burst The amount of suspended solids within a system changes due to plant conditions. Some events will release large amounts of solids (typically corrosion products) that result in suspended solids within the system. Releasing large amounts of corrosion products is termed a crud burst in the reactor coolant system. Several types of events or evolutions may cause a crud burst, including; reactor scrams, cooldowns, heat-ups, and reactor coolant pump starts. These evolutions will tax the demineralizer system with excessive corrosion products and personnel should monitor the effluent during cleanup efforts. The following are likely: ο· The demineralizer will filter the increased suspended solids from the crud burst. ο· The increased material will cause increased obstruction to flow, causing the inlet pressure to increase. Oil Contamination Another potential hazard for demineralizer resin beds is oily water. The oil will affect the exchange sites and render the resin ineffective. Oil will create a film on the resin beads that will block or inhibit the resin exchange 20 Rev 1 sites from performing their intended function since oil is an organic compound. Knowledge Check Prior to a scheduled nuclear power plant shutdown, the reactor coolant system was chemically shocked to induce a crud burst. What effect will this have on the purification demineralizers? A. Decreased radiation levels around the demineralizers B. Increased flow rate through the demineralizers C. Decreased demineralizer outlet conductivity D. Increased pressure drop across the demineralizers Knowledge Check A nuclear power plant was operating at steady-state 100 percent power when the reactor coolant system experienced a large crud burst. After ten minutes, the operators began to record parameters for the in-service reactor coolant purification ion exchanger. Assuming no additional operator actions, what trend will the recorded parameters show during the next few hours? A. Increasing flow rate through the ion exchanger B. Increasing pressure drop across the ion exchanger C. Increasing ion exchanger inlet water conductivity D. Increasing ion exchanger outlet water conductivity Knowledge Check Which one of the following, if processed through a demineralizer, will rapidly reduce the effectiveness of the demineralizer? Rev 1 A. Condensate B. Oily water C. Radioactive water D. Makeup water 21 ELO 1.8 Saturated Demineralizer Introduction A demineralizer is termed saturated when the resin beads are loaded with positive or negative ions. Saturation essentially biases the resin so that it will have a reduced affinity for certain ions. This can occur upon exposure of an ion exchanger to an overabundance of either hydroxyl or hydronium ions while in service. When a resin bead has collected all the unwanted ions that the resin bead can support, the bead is termed saturated; this is common toward the end of the bead’s service life. For example, as an R+OH- resin bead attracts Clions, the resin bead sites fill with Cl-. This is not a problem as long as personnel and conditions maintain the resin bead conditions constant. However, increasing the bead temperature will release some of the Cl- ions back into solution. This breakthrough can change the chemistry of the effluent and subsequent process chemistry. Saturating a resin bed effectively changes the affinity for ions of the whole bed and can be used to buffer changes in coolant chemistry. There are two types of demineralizer saturation discussed in this lesson. Boron Saturation In PWRs, during lower temperatures, the borate ion bonding to the resin exchange sites contains three boron atoms, while at higher temperatures only contains one atom. Lower-temperature resin will remove more boron and is much more efficient. Lowering the temperature of influent may increase the affinity for a particular ion such as boron. The lower the temperature, the more boron the resin will hold. If the temperature is increased, the resin affinity changes and the resin releases some boron. It is important to consider influent temperature when operating a demineralizer in a PWR that uses boron in solution during changing conditions of the purification system. Changing the efficiency of the resin will not only have an effect on coolant pH, it can have a direct effect on the boron in solution and consequently the reactivity and power. Lithium Saturation In PWR's, reactor coolant chemistry is maintained slightly basic in order to inhibit corrosion in the primary system. A pH of approximately 6.8 can be achieved by maintaining a balance between boron and lithium concentrations. At the beginning of life, the boron concentration is high. Therefore, to balance pH, personnel must maintain the lithium concentration high. To achieve an excess of lithium, resin beds are saturated when placed in service. There are normally two ion exchangers in the coolant purification system. Initially, both ion exchangers contain the same quantity of resin in 22 Rev 1 the form of Li+ and OH-. Initially, lithium concentration is increased to saturation in one of the coolant purification ion exchangers in order to aid in reactor coolant system pH control by preventing a large swing in lithium concentration and subsequent pH when placed in service. The addition of lithium-7 directly to the reactor coolant system is required if there is a high makeup requirement in the reactor coolant system, or if there is an initial lithium ion deficiency in the ion exchanger of the coolant purification system. During normal power operation, the boron-10 reaction produces lithium-7. A subsequent ion exchanger unsaturated with lithium removes excess lithium as a second step in coolant purification. Knowledge Check What is the reason for bypassing a demineralizer due to high temperature? A. Resins expand and restrict flow through the demineralizer. B. Resins decompose and restrict flow through the demineralizer. C. Resins decompose and create preferential flow paths through the demineralizer. D. Resins decompose and contaminate the system. Knowledge Check A nuclear power plant is operating at 70 percent steadystate power level when the temperature of the reactor coolant letdown passing through a boron-saturated mixed-bed ion exchanger is decreased by 20°F. As a result, the boron concentration in the effluent of the ion exchanger will ____________ because the affinity of the ion exchanger for boron atoms has __________. Rev 1 A. decrease; increased B. decrease; decreased C. increase; increased D. increase; decreased 23 Demineralizers and Ion Exchangers Summary Demineralizers and ion exchangers are passive components that have a major effect on system performance by maintaining the system chemistry stable and reducing the immediate effects of chemical excursions. Ion exchange is an exchange of ions between two electrolytes or between an electrolyte solution and a complex. During regenerations, a distribution system immediately above the resin bed introduces concentrated acid or caustic diluted with water to approximately 10 percent to the demineralizer. The regenerating solution flows through the resin. Personnel often use the decontamination factor (DF) as a guide for determining when resin bed is exhausted. The DF is the inlet conductivity divided by the outlet conductivity, expressed as a percentage. A demineralizer is termed saturated when the resin beads are loaded with positive or negative ions. This essentially biases the resin so that it will have a reduced affinity for certain ions. Now that you have completed this module, you should be able to demonstrate mastery of this topic by passing a written exam with a grade of 80 percent or higher on the following TLO: 1. Explain demineralizer operation and its effect on power plant operation. 24 Rev 1