NUPT-215

Nuclear Plant Chemistry unit 4

Bismarck State college
Welcome to chemistry NUPT-215

Instructors name
Principles of water treatment

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Overall Objective: without reference, explain the concept and application of ion-exchange in water purification. Enabling objectives: List the three reasons for removing impurities from water prior to use in reactor systems. Define the following terms: ion-exchange Demineralize Cation Anion Polymer Mixed-bed demineralizer Affinity Decontamination factor Describe: the following Resin bead Cation resin Anion resin Discuss the following factors of ion-exchange Relative affinity Decontamination factor Write the reaction for removal of NaCl and CaSO4 , by a mixed-bed ion-exchanger such as one containing HOH resin. Explain the three basic methods used to remove dissolved gases from water. List five filtration mediums used to remove suspended solids from water. Explain how mix-bed exchangers may be used to control pH. Explain the concept of reverse osmosis. 2

Water treatment; non-radioactive: (principles of ion exchange)

There are three major reasons for water treatment: To minimize corrosion, this is enhanced by impurities. To minimize radiation levels in the reactor facility. To minimize fouling of heat transfer surfaces. Water treatment begins when local water sources first enter the plant site. The first purification steps are taken here by mixed bed or layered type demineralizers. Mix-bed means that both cation and anion resins are mixed in the tanks and separated in the layered type. These tanks, valves, resin and piping allow for regeneration of the resin beads, back flushing, fluffing, and rinsing. Normally, these systems allow for one train to be on line at all times and are monitored by the auxiliary operator throughout his watch. Outlet alarms of high conductivity are sent locally and to the control room. Charting output is continuously monitored and can alert the operator when regeneration of the resin bed is required. Below is an illustration of demineralizer units.

Layered type demineralizer: Below is a layered type demineralizer which has separated anion and cation beds. This type has the advantage of easier regeneration as screens keep the beds separated. The input of caustic and acid are always in the correct location as the beds are held in the same spot.
Inlet water to be purified

Sight glass

Control Panel

Inlet float type flow meter

Anion bed, 60% by volume

Cation bed, 40% by volume

HCl or sulfuric acid used to regenerate the cation bed.

NaOH used to regenerate the anion bed

Resins are reversible ion-exchange devices. This means is that when an cation bed is exhausted, and all of its H + Ions have been exchange with other unwanted ions, the resin can be regenerated by injection of a strong acid. The highly concentrated acid solution will replace the unwanted ions with new H + ions. ( remember le Chatelier's principle).

 The same holds for the anion bed, so when regeneration is completed all the unwanted ions have been removed from the resin and flushed into a holding tank for neutralization and discharge Enlarged picture of resin beads

An ion-exchange resin or ion-exchange polymer is an insoluble matrix (or support structure) normally in the form of small (1 2 mm diameter) beads, usually yellowish, fabricated from an organic polymer substrate. The material has highly developed structure of pores on the surface of which are sites with easily trapped and released ions. The trapping

of ions takes place only with simultaneous releasing of other ions; thus the process is called ion-exchange. There are multiple different types of ion-exchange resin which are fabricated to selectively prefer one or several different types of ions. (affinity)

Ion-exchange resins are widely used in different separation, purification, and decontamination processes. The most common examples are water softening and water purification.

Cation exchange: (cations in the water coming in) These ions are removed by the (strong acid) cation beads. The cation beads exchanges H+ ions for the positively charged cations in solution. The order of preference is Ca++, Mg++, K+ and Na+. The released H+ will link up with the companion ions of the exchanged ions or OH- ions (in mixed beds). For layered units strong acid can form and this is why you will find these tanks, valves and piping lined with rubber. You do not want any corrosion occurring between the tank and the rubber lining and the tank. If this occurs the rubber will break lose and cause a system outage You will normally find some type of anodic protection on the tanks As you can see by Na+ being the least desired of the cations, it is the least closely bound to the resin. When regeneration time is getting close the Na+ ions will start to leak off the resin. As it turns out, this benefits operators and chemist monitoring the effluent that resin exhaustion is ready to occur. The conductivity reading will begin to spike after a slight drop. Strong acid cation resin is used a most nuclear plants.

Lets look at an exchange example for a cation resin using NaCl and CaSO4 NaCl + H2 O Na+ + Cl These ions then pass into a cation and anion bed. In the cation bed, designated as H-R you have the following reaction (the R represents resin) H-R + Na+ Na-R + H +

Anion exchange: (anions in the water coming in) These ions are removed by the (strong base) anion bed. The anion bed exchanges OH- ions for the negatively charged anions in solution. The displaced OH- ions will react with the acids formed in the cation bed or H+ to form water. The anion resin can pick up organic compound that are not removed during regeneration. This condition can be recognized by shortened regeneration cycles. The organic compounds take the exchange sites that would carry the OH- ions after regeneration. Sometimes treatment with formaldehyde will rid the organics but not always.

For the Cl ion, when it goes through the anion resin R-OH + Cl R-Cl + OH Thus removing the unwanted ion Cl and generating an OH ion. The nice result of this is the hydrogen ion and the Hydroxyl ions will combine to give us pour water. H + + OH H2 O See if you can figure out what happens with the CaSO4 Because your first job as an operator or chemist will most likely include taking care of the plant demineralizer system we have incorporated the regeneration of the resins in a mixed bed system. Regeneration of ion exchangers: In the following drawings and description, and regeneration is described. For entry level operation and chemistry positions, you will become very familiar with this operation.

This first drawing is of normal flow through the demineralizer. Note that the incoming water is routed to the top of the tank and meets the anion beads first. If it is a mixed bed there will be some cation beads mixed in.

The next step in regeneration is the back wash. Water is routed in the bottom of the tank and removes debris and suspended solids that were picked up during the run. The outlet water goes to a collection tank which will be treated before discharge. The valves shown in these drawings are manual valves. In actuality, at nuclear plants, the valves are air actuated diaphragm valves which are automatically controlled during the regeneration. These drawings are just illustrations to show you the system flow changes

To demineralizer waste tank

After the back wash, the resin will be separated with the anion beads on top and the cation beads on the bottom ( If it is a layered unit, the beads are separated by screens). Caustic is then injected into the anion beads and because ion exchange is reversible the captured ions are released and the sites in the resin are replaced with the OH- ions. (Remember le Chateliers principle) Remember that the top and bottom of the tanks have screen installed to prevent losing the resin beads. Strong acid either sulfuric or HCl is injected into the cation beads. The captured ions are released and replaced with H+ ions. Acid Caustic

to sample recorder Demineralizer waste tank

To plant effluent discharge after neutralization Mixing motor

The next stage is the slow rinse. This removes the excess acid and caustic as well as the unwanted ions to the drain tank.

In the vent and partial drain, room is made for air injection in mixed bed units. This step is not required in layered units.

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For mixed bed units, this is a very important step because it is for mixing the resin beads in the tank to re-establish the mixed bed function. This step is also called fluffing at some nuclear plants. The air volume used in mixing is critical because there has to be enough to mix the beads but not enough to damage the screens holding the resin.

In this stage, a final rinse is performed and the effluent is monitored until the output meets the required specifications. < 0.2 S/cm, < 0.003ppm Na, < 0.005 ppm Cl. At most nuclear plants. Once the specifications are met, the unit is placed back in the run status that we started with above.

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Common troubles with this system: Loss of resin beads in effluent. ------ Failure of retention screens. Flow loss or reduction in output flow------ rubber lining detached. Increased rate of required regeneration. o Improper regeneration settings. o Change in supply water specifications such as over chlorination by suppliers. o Fouling by organics, caused by improper ground water chlorination. o Bead natural ware causing loss of exchange sites. o Poor quality of regeneration reagents (acid and caustic).

Channeling is the process of resin tunneling by the influent water. It bypasses the resin beads and is not properly treated. The way of avoiding this condition is by normal regeneration o Breakthrough and exhaustion. Breakthrough is a condition in which unwanted ions start to leak from the resin. After breakthrough, exhaustion is not far behind and the resin will stop doing its assigned task and must be regenerated.

Condensate Polishers:

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The feed water system uses another set of ion exchangers that are used to clean and purify the water condensed from the turbine exhaust steam. This water is then used to feed the steam generator in a continuous cycle of cleaning and re-injecting the feed water into the steam generators. Prior to re-use, the condensate must be purified or "polished", to remove impurities which have the potential to cause damage to the steam generators, reactors (BWR) and turbines. Both dissolved (Example. silica oxides) and suspended matter (Example. iron oxide particulate), as well as other contaminants which can cause corrosion and maintenance issues are effectively removed by condensate polishing treatment.

At most plants, when the exchange capacity of the resins are exhausted or a high differential pressure exists, the "spent" resin is transferred (called sluicing) to an external system for separation, backwashing and regeneration. This operation is critical because loss of polisher flow or miss-operation of valves can cause a reactor trip and loss of feed water to the steam generators. Condensate polishing differs from regular ion exchange in that ion exchange is only part of the overall process as the condensate is already of high quality and only requires polishing. The other main function of condensate polishing is to physically filter corrosion products from the steam condensate. A properly functioning condensate polisher is therefore just as likely to require back washing and regeneration based of increasing pressure drop, as it is based on ionic exhaustion. The ion exchange of the process involves exchanging the contaminant ions with hydrogen and hydroxide ions (for H-OH cycle) in a porous synthetic resin media just like the demineralizers we talked about earlier...

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This is a picture of parallel condensate polishing units at a power plant.

This is a simple illustration of the external resin regeneration system used at some plants for the condensate polishing units

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Let down ion exchangers used in the primary system (Radioactive)

The AP1000 CVCS by Westinghouse. The ion exchangers are marked by the red box. This has one ion exchanger for deboration, one ion-exchanger reserved for LiOH removal and one used for general RCS cleanup and purification.

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The resins used in these tanks are not regenerated during the fuel cycle. If they fail or exceed radiation dose limits for some reason, the resin is replaced. These resins become highly contaminated and have to go offsite as radwaste. The design and chemical makeup these resin beads are Site specific and information about them are protected by the suppliers. This is why there is little in your text about the subject. Most PWR nuclear power plants use mixed bed resins tuned for specific ions; Having a relative affinity for the specific ion to be removed. Most let down ion-exchanges have a ratio of 1:1 anion to cation. Most BWR plants use powdered resins (So called Powdex) although some use mixed bed resins. Temperatures of most operating beds are in the 1000-1200 F range, 1400 max. Principal radionuclides trapped on resins are 58Co, 60Co, 134CS, 137CS, and 54Mn. Radionuclide loading should not exceed 10Ci/cuft. The organic polymer structure begins to be damaged by radiation at the 108 rads point. Spent resins are normally mixed with concrete in 55 gal drums or larger steel vessels before shipping off site for disposal.

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Decontamination factor for ion-exchangers: (applies to all ion exchangers) This factor is just a measure of what item you are interested in removing or controlling. Then dividing what goes in by what comes out. For example: Conductivity Boron

The higher the number the better the ion-exchanger is working

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Spent fuel pool ion-exchange system: Because spent fuel elements and rods must be maintained in a chemically sound, cooled, and corrosion free environment, the spent fuel pool has a cooling system (for removal of decay heat) and ion-exchange system for purification of the pool. These ion exchangers are mixed bed H-R and R-OH types that are not regenerated but instead replaced when the resin is exhausted. Usually these resins are Highly radioactive and are treated as the letdown ion-exchanger resins are.

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The spent fuel pool is approximately 40 ft. deep for shielding purposes. The blue light is caused by particles exceeding the speed of light at the fuel clad surface water interface.

If you ever get a chance to go see this,. dont let it go, because a picture does not do it justice.

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Reverse osmosis: (RO) Is a method that removes many types of large molecules and ions from solutions by applying pressure to the solution when it is on one side of a selective (semipermeable) membrane. The result is that the solute is retained on the pressurized side of the membrane and the pure solvent (water) is allowed to pass to the other side. To be "selective," this membrane should not allow large molecules or ions through the pores (holes). In the normal osmosis process the water naturally moves from an area of low solute concentration,

through a membrane, to an area of high solute concentration. The movement of pure water to equalize concentrations on each side of a membrane generates a pressure and this is the "osmotic pressure." Applying an external pressure to reverse the natural flow of pure water, is reverse osmosis. The process is similar to membrane filtration. However, there are key differences between reverse osmosis and filtration. The predominant removal mechanism in membrane filtration is straining, or size exclusion, so the process can theoretically achieve perfect exclusion of particles regardless of operational parameters such as influent pressure and concentration. Reverse osmosis, however, involves a diffusive mechanism so that separation efficiency is dependent on solute concentration, pressure, and water flux rate (amount of water passing per square unit).
Reverse osmosis is most commonly known for its use in drinking water purification from seawater, removing the salt and other substances from the water molecules. However, RO units are starting to show up at many nuclear power plants as a preconditioning system prior to going through the demineralizer systems to minimize cost of chemicals and labor needed for regeneration and testing. In addition, nuclear plants located next to salt water bodies can effectively convert sea water for input to the DI water plant and limit use of ground water supplies. On the next page is a picture of an industrial RO unit consisting of multiple semi-permeable membranes.

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Several units of this type ganged in parallel can supply sufficient pure water for input to the in plant DI system.

Below is a cross section of a semipermeable membrane material. The material used can vary but in any case the material lets pure water through but stops larger molecules and ions from going through. As efficiency and lower cost for materials are achieved, more units will be used at most nuclear sites.

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Salt water reverse osmosis unit diagram.

Schematic of a reverse osmosis system (desalination) using a pressure exchanger. 1: Sea water inflow, 2: Fresh water flow (40%), 3: Concentrate Flow (60%), 4: Sea water flow (60%), 5: Concentrate (drain), A: High pressure pump flow (40%), B: Circulation pump, C: Osmosis unit with membrane, D: Pressure exchanger Below is a cut away drawing of the pressure exchanger which is basically a rotary piston pump using the force of the reject water to increase the pressure for the high pressure pump.

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A: High pressure side B: Low pressure side C: Rotor rotation D: Sealed area 1: High pressure reject water inflow 2: Pressurized sea water 3: Low pressure sea water inflow 4: Low pressure reject water drain : Reject water / concentrate : Piston / barrier : Sea water

Remember to read the text, lecture notes prior to taking your exam

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