NUPT-215

Nuclear Plant Chemistry unit 3

Bismarck State college

Welcome to chemistry NUPT-215 Unit 3

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Unit 3: reactor water chemistry

Objective: without references, describe the effects of radiation on reactor water and methods of treatment for products.

Above is a typical Westinghouse 2 steam generator reactor coolant system. This is a high pressure, high temperature, and high radiation system that will affect the reactor water chemistry.

Unit 3.1: effects of radiation on water chemistry (synthesis)

Describe the process of radiolytic decomposition and recombination of water, as well as activation products and half-life of cobalt 60. Describe the process of radiolytic decomposition and recombination of nitric acid and ammonia. Note: these substances are no longer used in the primary coolant. Any recombination or radiolysis does not have a major impact on pH. State the advantage of maintaining excess hydrogen in reactor water. State the three sources of radioactivity in reactor water and each ones decay product. Be able to state parameters monitored and how the are controlled. Be able to sate secondary parameters monitored and how they are controlled. Describe how pH is controlled and its relationship with Boron.

An operating reactor core is an area of very intense radiation fields; this radiation affects the chemistry of the water and other substances moving through the core. Before we dive into the interactions that occur, we need to review what radiation is and what the different types are. Reactor refueling bridge over the core

Radiation types: Alpha () : consists of 2 neutrons and 2 protons with no electrons. It is a very direct ionizing radiation that is not vary penetrating. After stealing electrons, it becomes a Helium atom. Usually contained by in fuel. Beta (- ) : is a high energy electron not held in any atoms shell.

Positron, (+ ) : is an anti-electron that is the direct ionizing type. Annihilates . when it meets other matter. Does not last very long before . annihilation.
Gamma () and X rays: are high energy electromagnetic waves that are very penetrating. Has no charge, is not a direct ionizing radiation. Neutron, (): has a neutral charge, Very penetrating, and causes fission. is not a direct ionizing type. Proton, (): Has a +1 charge. some what penetrating. is a direct ionizing type. Other particles and rays will not be covered, as they are outside the scope of this course. Water decomposition: H2O + Radiation e- + H2O+ This is the equation listed in the class text Creates an ion-pair. Very reactive chemically after decomposition.

 Below is a representation of a water molecule which will demonstrate what happens with radiation decomposition. Remember the equation H2O + Radiation e- + H2O+ In this example its a gamma ray causing the problem Gamma ray

2 + The gamma rays energy was completely absorbed by the electron. The excitation energy now exceeds the binding energy of the nucleus and the electron is ejected becoming a beta minus particle. This particular example is called the photo electric effect. What is left, is an ion-pair, the e- and the H2O+

 A majority of water decomposition in the core is caused by gamma rays through the photo electric effect(our example) or Compton scattering, in which the gamma has sufficient energy to not only eject the electron but continue on (scattered) at a lower energy level. The ion-pair then go through parallel and various reactions ending with 22 O + radiation 22 + 2 A summation of the various ionic components involved in the pathway of water decomposition is a follows: 4.9 2 O 2.7 + 2.7 OH + 3.4 + + 0.7 O + 0.45 2 + 0.75 2 2 + 0.6 H Recombination of the oxygen occurs by keeping a surplus of hydrogen in the RCS Proton ionization: this reaction takes place when a proton forms an ion pair; as the gamma ray does, except in this case, the electron is stripped by the proton. The proton comes from any element that is struck by a neutron and knocks out the proton from the nucleus. The high energy proton with its + 1 charge then passes into the area of orbiting electrons of another element (water molecule). The proton then attracts an electron to form hydrogen thus stealing an electron or it can add enough energy to the electron causing an ejection forming an ion pair or a water ion. Below is an animation of the event.

 Below is a representation of a water molecule which will demonstrate what happens with proton radiation decomposition. Remember the equation H2O + Radiation e- + H2O+ Proton particle

2 + In either case, the water molecule is left as an 2 + ion.

Hydrogen addition: with the production of 2 produced by the various reactions described above it is necessary to use hydrogen to control the corrosion causing oxygen. Hydrogen level is maintained at 2.2 4.4 ppm at most plants. By maintaining this level, the extra oxygen produced by radiolytic decomposition is rapidly consumed and that oxygen injected in the makeup water is also kept low (<0.01 ppm). The equations are forced to the left. (Remember Le Chatelier's principle) The upper limit on hydrogen is to prevent Zicaloy embrittlement and other absorption problems from happening by excess hydrogen present in the coolant.

With the introduction of the various gases into the Reactor Coolant system (RCS) it can become necessary to remove these gases to keep them in specification. This is accomplished by a couple of methods (depending on plant type). These methods are described below and animated for review. The drawings used are only general in nature and change from plant to plant, but the concepts are the same at all the plants. However, in order to understand chemistry control, they must be introduced at this time. Below is a drawing of a single loop of the Pressurized Water Reactor (PWR) and the secondary steam side of the power plant. This is a vary simplified drawing but useful for explanation of chemistry control.

In order to remove excess gasses (called degassing) two methods are shown below. in each case the gasses are removed in the Chemical and Volume Control System (CVCS). The pathway for these are shown. Normal RCS flow Degassing from pressurizer to CVCS (not at all plants) Pressurizer spray flow, used to control primary pressure. RCS letdown flow to CVCS Feed water and steam flow

To CVCS To CVCS degassing degassing system Pressurizer steam space Pressurizer heaters

Main steam

Feed flow

Letdown flow to CVCS for degassing and purification

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Total gas: is the sum of all the gases that are in the RCS coolant. If total gas gets too high, it could damage pump impellors or even cause pump cavitation making it useless. To prevent this, system degasing is periodically required by either venting from the pressurizer or by degasing the letdown. If all the gases are kept in specification, it will not cause any pump damage. Hydrogen and oxygen specifications and control: The hydrogen limits are 2.2 4.5 ppm. The low limit is based on having enough hydrogen for oxygen removal. The upper limit is in place to prevent zirconium embrittlement ( the fuel clad is made of Zr). When the plant is shutdown (< 2000), Hydrazine is used to control O2. Hydrazine is an inorganic compound, formula H4N2. It is toxic and flammable so take all precautions when you see or use it. Hydrazine is added as needed to keep O2 levels in specifications. The oxygen limit is <0.01 < 0.005 ppm depending on which plant. This limit is in place to prevent general and other O2 dependent corrosions. Note: that by maintaining a positive hydrogen concentration in the RCS radiolytic decomposition is also minimized.

For degassing of Nobel Gases and Hydrogen: The previous animation showed flow from the RCS going to the CVCS. In the next animation we will see where this flow comes into the CVCS and how gas is handled there. It should be noted again that different plants have slightly different designs for their CVCS but the concepts are the same. Let down flow goes through the ion exchanger as for normal purification but is diverted at the VCT to the pre-holdup ion-exchanger. It then goes through a filter before going to the gas stripper. The gas stripper heats the flow and passes steam through it to remove the gasses that then pass to the cooler, charcoal filter. the activity monitor, and to atmosphere. The effluent is returned to the VCT or the hold up tank.

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Activity monitor

Charcoal filters

Gas cooler

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Radionuclides in the RCS due to radiation effects: Note: The text requires to state the three sources of radioactivity in the RCS and their decay products. This is inaccurate to say the least. for testing purposes the ones listed in the book may be used, however, the list given here is more accurate. Also understand that in actuality their are many more than listed here because of recoil fission products that actually make up the bulk of radionuclide activity loading after a reactor has operated for a length of time.

Below is a list of activated elements to be expected during normal spectroscopy analysis of the primary coolant along with their half- lifes:
Activation 16O (n,p) 16N 16O (p,) 13N 18O (p,n) 18F 10B (n,) 7Li (n,n) 3H 10B (n,2) 3H 6Li (n,) 3H 7Li (n,n) 3H 14N (n,p) 14C 17O (n,) 14C 40Ar (n,) 41Ar 35Cl (n.p) 35S 35Cl (n,) 32P 32S (n,p) 32P 31P (n,) 32P 2H (n,) 3H Half life 7.13 s 9.96m 109.7 m 12.3 a 12.3a 12.3a 12.3a 5730 a 5730a 1.83h 87.5d 14.3d 14.3d 14.3d 12.32a

The way to understand these nuclear notation formulas can be shown by the following example: 16O (n,p) 16N resulting isotope Original isotope, Initiating particle, resulting particle. s = seconds m = minutes h = hours d = days a = years

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Activated corrosion products: (crud) 59Co (n,) 60Co 5.27a 58Ni (n,p) 58Co 70.9d ( this isotope is an anti-electron emitter) 54Fe (n,p) 54Mn 312.1d 56Fe (n,p) 56Mn 2.57 h 58Fe (n,) 59Fe 44.5d 123Sb (n,) 124Sb 60.20d There are other activated elements, but they play an insignificant dose rate factor or their half-life is so short as to not play any major part in radio chemistry.

Below is an example of plant isotope loading in the RCS letdown stream of an operating power plant. Note all the recoil fission products or fuel leakage products. Tritium, an activation product, is number 12 on the list. These listings are similar for most PWRs

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Chemistry parameters: Objectives

State the following for reactor water chemistry. Nine parameters controlled Reason for controlling each parameter. Method of controlling each parameter. State the possible effects of abnormal chemistry on core conditions

pH and pH control: At an operating PWR the reactor is loaded with excess enriched uranium U-235 at the refueling or original load. To prevent having more control rods to control reactivity, a chemical shim is added to the RCS coolant to control the additional reactivity of the fuel load.

This chemical shim is boric acid (H3BO3). The B10 enriched boric acid loves to absorb neutrons and thus helps control the nuclear reaction. The problem is the second term of this chemical; acid. Whenever boric acid is added, it tends to lower the RCS pH which, as we have learned, increases the corrosion rate. Below is the nuclear formula for a particle ejection after absorption of a neutron by boron-10
1 0

+ 10 5

11 5

7 + 4++ 3 2

LiOH and pH control: The pH range desired at PWRs is 6.9-7.4. In order to accomplish this , LiOH is added to the RCS. LiOH is a base and therefore will raise the pH when added. The LiOH uses enriched Li7 because as we discussed previously the by product of the boron-10 reaction with a neutron yields Li-7 + an alpha. In this way, the plant will be dealing with the same lithium-7 making removal by ion-exchange easier

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 There are limits on the use of LiOH between 0.2 and 2.2 ppm, these limits are base on zirconium and Inconel stress corrosion. In other words, pH is determined by the balance between boric acid and LiOH with their associated limits of concentration. The upper limit concentration for boric acid is about 2200 ppm to prevent the core from having an insufficient margin to a positive temperature reactivity coefficient. The LiOH and boric acid concentration decrease over core life as the fuel is burned up and by still maintaining a pH of between 6.9 and 7.4 Note: the text book lists Nitric acid and ammonium hydroxide as pH control agents, this is incorrect. How is LiOH and boric acid placed in the RCS? Both boric acid and LiOH concentrations are maintained using the CVCS. Both are injected into the primary coolant using the CVCS. Both are removed using the CVCS ion-exchangers or routing of letdown coolant flow using the CVCS. See what they look like below. Lithium hydroxide Boric acid crystals

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Here is an older Westinghouse reactor CVCS system. Note it is similar, but not the same as their new AP1000 CVCS shown above. On first click, the flow for boric acid addition will be shown. The boric acid is of a 7000 ppm concentration and does not pass through the VCT nozzles due to the plugging potential. Injection is stopped when the required RCS value is obtained. On second click, the LiOH addition, and hydrazine addition path will be shown.

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O2 control and hydrogen addition: Oxygen, the ultimate corrosion bad guy, must be controlled < 0.01ppm or <0.05ppm for Westinghouse plants if possible by use of hydrogen addition when at power and hydrazine when shut down < 2000 F. Whether the O2 comes from the radiolysis of water through its decomposition or is injected in makeup water, it still needs to be removed.

As stated earlier, hydrogen is added to control oxygen. Once again the CVCS is used to add the required hydrogen as well as hydrazine. look at the CVCS below.

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 In the green circle there are two gas valves. One is a hydrogen supply valve to the VCT and one is a nitrogen supply valve to the VCT If the hydrogen content in the RCS is low, operations will charge the VCT with hydrogen which will saturate the coolant with hydrogen and is injected with the returning water. Once the concentration required is obtained, the hydrogen will be cut off and a nitrogen blanket will be established, if required, in the VCT. Hydrazine is used to control oxygen concentration when the RCS temperature is < 200 degrees F. This chemical is injected in the same manner as LiOH was in the previous section using the chemical addition pot. Conductivity: this level is maintained by use of the letdown demineralizer or if required, feed and bleed. Conductivity is a measure of the reactor coolants ability to conduct electricity. At PWRs the conductivity is set by the concentration of the Boric acid and LiOH in the system. Once these concentrations are established, a base line conductivity reading is set and then monitored for any off-normal readings. Off-normal readings of conductivity may require corrective action to be taken in order to limit scale formation. Off-normal readings may also indicate increased corrosion rates taking place. Spent fuel pool conductivity is maintained less than 20 siemens/cm and sampled no less than weekly with annual calibration of the conductivity meter required. ( NRC requirements) Chlorides: To preclude chloride stress corrosion levels are maintained less than 0.15 ppm. This level is maintained by use of the letdown demineralizer or if required, feed and bleed operations.

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Fluorine: To preclude corrosion of Zr cladding of fuel rods. Maintained < 0.15 by demineralizers or feed and bleed. Boron: Concentration is dependent on excess fuel loading but must be maintained less than 2200 ppm to insure negative temperature reactivity coefficients. Added and removed as required by the CVCS. Produces Li-7 when a neutron is absorbed. Boric acid tends to lower pH and is countered by the addition of LiOH. Boric acid is not borax. Radioactivity in the reactor coolant: Please Ignore the text book on this particular issue. Radioactivity is continually monitored by various process monitors and periodic sampling of the reactor coolant. Actual activation of reactor coolant constituents and fission recoil products were listed and described in an earlier section. Tritium: (3H) The primary sources of 3H is Boron, lithium and activation of 2H. because deuterium only constitutes 0.015% of natural water, it is a smaller contributor of tritium than boron and lithium. The problem with tritium. It has a long half- life It penetrates into materials It sticks to boron and is picked up in the letdown demineralizer It can pass through piping into containment It can come out of solution during refueling outages or any time a primary system is opened. It emits Bata radiation, can be inhaled; and taken into the body.

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Abnormal chemistry conditions: O2 injection: can be caused by accidental addition of non-de-aerated water. This causes a depletion of hydrogen and resulting drop in pH. Increased corrosion will result including possible crud burst. Resin Overheating: must be avoided because of several reasons: It will release all the undesired substances that it had captured It will release chemicals that mask the readings of other chemicals such as chlorine. It will cause failure of the resin beds to work as designed It makes the coolant smell like dead fish.

Fuel element failure: Failure will be detected by spectrometry showing the presence of increased concentrations of 131I, 137Cs, or by gas counter of 133Xe and 85Kr showing a steep rise in activity. These are all fission products of 235U. After shut down, the failed rod can be found by ultrasonic testing and removed from the core. It will cause large changes in the normal radioactive readings.

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Tube failure in steam generator: While operating at power, a leak in a steam generator tube may not show obvious volume changes in the RCS level instruments. In fact, a majority of such leaks in the industry manifests itself in this fashion. The way tube leaks are discovered is by periodic testing or process monitoring of the secondary system water for radionuclides. Fission products, cobalt-60 &59 etc. would start showing up in the secondary. In these slow leaks, it is usually because if a stress cracking corrosion problem at one of the tube to tube sheet welds. A tube rupture on the other hand, will be seen as a reactor coolant leak with changes in the pressurizer water level. Immediate action would be required to shut down the plant. Radiation alarms would be set off on the secondary water system, And means taken to prevent any discharges off site.

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PWR primary coolant specification: O2 <0.01ppm or <0.005ppm WH H2 2.2 - 4.5 ppm or 2.2- 4.4 ppmWH Cl < 0.15 F <0.15 SiO2 < 0.2 Conductivity LiOH & B concentration pH 6.9 7.4 Suspended solids <0.35ppm LiOH 0.2 2.2ppm Su <0.1 Al <0.005 WH Ca < 0.005 WH Mg < 0.005 WH BWR Normal water chemistry values: Conductivity Cl SO4 Zn O2 SiO2

PWR secondary system (S/G) feed water O2 <0.01ppm <0.005ppmWH n/a Cl < 0.01ppm ,0.005 WH n/a SiO2 < 0.01 ppm BW n/a 9.3 Cu <0.001ppm N2H4 < 0.1ppm SO4 < 0.003 ppm BW

.11 S/cm 1ppb 2ppb 5-10 ppb 10ppb with H2 addition 200ppb w/o < 100ppb

Spent fuel pool chemistry specifications at most plants

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Spent fuel pool chemistry for a particular plant but will be similar to most others Water Parameter pH Quality Operating Limit 5.5 to 8.5 Monitoring Frequency Weekly

Conductivity
Activity

10 mS/cm
Cs-137: 500 dpm/ml Alpha: 3 dpm/ml Tritium: 0.4 mCi/ml (8.88 x 105 dpm/ml) (Cu) (Hg) (Cl) 0.1 ppm 0.014 ppm 0.1 ppm 1.0 ppm

Weekly
Weekly Monthly Biannual Biannual Biannual Biannual Biannual

Copper Concentration Mercury Concentration Chloride Concentration

Iron (Fe) Concentration

Aluminum Concentration Temperature Boron

(Al)

1.0 ppm 40 C/ 104 F 2,000 ppm

Biannual Weekly Weekly

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Spent fuel pool showing Cherenkov radiation

Fuel element assemblies placed in racks

Spent fuel pool bridge over the pool

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Secondary chemistry: Secondary water chemistry control during plant operation has an important effect on steam generator maintenance in pressurized water reactors. It can mitigate the degradation of the heat exchange coefficient or heat rate due to the formation of scale deposits and sludge accumulation in SGs. Chemistry control of the secondary is made harder by the fact that so many different metals and alloys are used in the whole system and must be considered. Materials, including stainless steel, nickel base alloy, and carbon steel which is very sensitive to erosion-corrosion are used. In addition, copper ion are also introduced by some materials. Because of the steam formation, high heat flux, and flow rates, induced concentration processes occur. Transport of chemicals in various proportions in the liquid and vapor phases according to the specific properties of the compound also complicate matters. With different temperatures and phases, some chemicals may highly concentrate due to the heat flux and hide out phenomenon. This makes the chemistry regulation of the various system parts a real challenge. On the next slide, is a simplified drawing (Figure 1) of a PWR secondary system.

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Notice the sampling points or monitors and what is being sampled

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Main steam from the S/Gs Main steam enters the turbine and passes to the condenser where it is now at vacuum and is condensed to water. If any condenser tubes are Leaking, the low quality cooling water will be pulled into secondary water and cause impurities to be added. The condensate storage tank Is filled from the plant Demineralizers and is sampled to insure specifications are met. This tank uses a N2 or steam blanket to prevent O2 absorption.

See unit 4, for more information on Condensate polishers (Ion-exchangers) Chemical addition tank for hydrazine and ethanolamine (ETA) Called All Volatile Treatment (AVT) when used together

Condensate booster pumps

Chemical injection pump

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Secondary water chemistry history and chemical control:

Lets take a look at some of the information we just covered on the chemicals used. But as we do, lets also take a look at the history of secondary plant chemistry history.
History: Sodium phosphate treatment was originally used for pH control and conditioning of boiler water. Some plants opted to control the phosphates at various levels within the allowable range. During condenser in-leakage, the phosphate and calcium ion reactions depleted the steam generator water of soluble phosphate, increasing the Na:PO4 molar ratio and forming free caustic. This resulted in an increased rate of Alloy 600 steam generator tubing stress corrosion cracking. Although different adjustments were made, corrosion attack continued. For example, wastage or local wall thinning was observed. Then , the new, all volatile treatment (AVT) using ammonia compounds were used for pH control of the feed water. Based on the data collected during the use of the new treatment, ethanolamine ( ETA) contributed to reduced transport of iron from the secondary system steam drain lines and a resulting lower concentration of iron in the feed water system without a significant increase in the concentrations of other impurities. This was facilitated by the lower volatility of ETA at high temperatures and the consequential increased concentrations in the steam drains as compared with other pH control chemical reagents.

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 AVT compounds: Ethanolamine (C2H7NO) (ETA or MEA) Morpholine (C4H9NO) Hydrazine (N2H4) Dimethylamine (DMA) Methoxypropylamine (MPA) Amoniumhydroxide (essentially no longer used) These different compounds are used either mixed or separately depending on the power plant. Below is a pie chart of usage by % of plant use. Remember, the goal is to limit the concentration of impurities in the steam generators. Prevent corrosion of the tubes by, support plates for the tubes, And to prevent scale build up and loss of heat transfer capabilities. The AVT chemicals provides for some carry over into the steam/water spaces thus helping to maintain a good pH.

This Pie chart shows the different amines used at PWR nuclear power plants by % of plants using a particular amine or mixture.

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Use of amines in the changing secondary chemistry: pH control Morpholine is losing favor as a pH control agent because it exhausts the condensate polishers at a faster rate than other amines. ETA is a less volatile agent and helps prevent Fe carry over to the steam generator and it affects the condensate polishers to a lesser degree. You can see from the chart that it is a favored pH control agent. A problem with ETA however, is that it causes a problem called denting at the tube sheet-tube area. It has been found that with the addition of 10ppm boric acid reduces the growth rate of corrosion products that cause the tube sheet problems. Using volatile chemistry means that as the water is turned to steam in the steam generators, less of the substance is left in the steam generator. Continuous blow down of the steam generators at power removes sludge and other impurities that collect in the steam generator. This is accomplished by a small line near the bottom which is opened for discharge to the condensate system. Each of the amines has advantages and disadvantages and an ongoing research program is underway to come up with the best chemical control program. O2 control in the secondary system: Hydrazine and other amines are added to the feed water system for O2 control. All efforts must be made to prevent air in leakage to the condenser water boxes to prevent O2 absorption into the feed water. Only de-aerated water should be added for make up to the secondary system Condenser tube leaks should be prevented at all cost since the pulling of undemineralized and oxygen bearing water into the water boxes introduces many impurities into the secondary system. Other controlled items: for the other impurities, condensate polishers are the means of control. For more information on condensate polishing see unit 4.

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This is the steam generator side of our first drawing:

Amines are volatile and do not collect in the steam generator.

All of these reheaters and feed heaters are a prime source for generating iron impurities. It was found that ETA reduced the amount of iron found in the heater drains.

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Boiling water reactor chemistry: There are basically 4 things that effect the BWR water chemistry The combined effect of boiling in the core with radiolysis of water forming O2, and H2O2 which creates an oxidizing environment. The feed water purity. The size and efficiency of reactor feed water cleaning systems The deposition of substances on the fuel surfaces. Originally, there was no water chemistry control at BWRs other than using highly pure and pH neutral water. This resulted in a condition known as Electrochemical Corrosion Potential (ECP). The results of this was an intergranular stress cracking corrosion. Concentrations of O2 in the reactor water ran in the 200ppb range and eventually was found to be unsatisfactory.

MHWC: along comes hydrogen addition Moderate Hydrogen Water Chemistry (MHWC), requires the addition of elevated levels of hydrogen to the reactor water for the scavenging of excess oxygen formed by radiolytic decomposition of water. Normally the H2 addition is in the range of 1.6 to 2 ppm. The problem with hydrogen addition is that radiation levels increase in the turbine building due to N16 migration. The chemistry control of BWRs as well as PWRs are still under testing and modification plant specific information will be available to you if you get a position in chemistry or operations. Zinc addition (zinc injection passivation) was found to reduce radiation fields on piping by reducing the corrosion rates. The zinc plates out on any missing sites or defects in the magnetite coating. Some plants have not seen any improvements. Thats the extent of special additions made. The rest of BWR chemistry is just maintaining very pure water standards.

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This completes this Presentation. Remember to perform the reading assignments in the text and lecture notes prior to taking the unit exam. Also note that the chemistry specifications for the different plants are listed in the lecture notes.

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