chemistry and radiation safety - amazon s3 · chemistry and radiation safety . technical advisory...

© 2016 Electric Power Research Institute, Inc. All rights reserved.

P. TranRadiation Safety & Deommissioning

Program Manager Monday, August 29, 2016

Chemistry and Radiation

Safety Technical Advisory Committee

Date: 8/15/2016

Pre Meeting Materials

AM Session

2© 2016 Electric Power Research Institute, Inc. All rights reserved.

Antitrust Guidelines for EPRI

Meetings and Conferences

The antitrust laws and other business laws apply to EPRI, its Members, participants, funders, and advisers;

violations can lead to civil and criminal liability. EPRI is committed to both full compliance and maintaining the

highest ethical standards in all of our operations and activities.

These guidelines apply to all occasions: before, during, and after EPRI meetings, including in the hallways,

over lunch, during breaks and at dinner.

…is to conduct research and development relating to the generation, delivery

and use of electricity for the benefit of the public. EPRI advisory meetings are

conducted to further that purpose.

…is to follow the meeting agenda and provide advice on EPRI’s R&D program

and how to make EPRI results most useful. Consult with your company counsel if

at any time you believe discussions are touching on sensitive antitrust subjects

such as pricing, bids, allocation of customers or territories, boycotts, tying

arrangements and the like.

EPRI’S PRIMARY PURPOSE

YOUR ROLE AT EPRI

ADVISORY MEETINGS



Meetings and Conferences (continued)

…pricing, production capacity, or cost information which is not publicly available;

confidential market strategies or business plans; or other competitively sensitive

information. Do not disparage suppliers and/or competitors of EPRI, technology

providers and/or EPRI Members and participants.

…the use of particular vendors, contractors or consultants for non-EPRI projects.

EPRI will not promote or endorse commercial products or services of third parties.

You must draw your own conclusions and make your own choices independently.

…in any discussions of goods and services offered in the market by others,

including your competitors, suppliers, and customers.

DO NOT DISCUSS

EPRI DOES NOT

RECOMMEND

BE ACCURATE, OBJECTIVE,

AND FACTUAL



Meetings and Conferences (continued)

…to discriminate against or refuse to deal with (i.e., “boycott”) a supplier; or to do

business only on certain terms and conditions; or to set price, divide markets, or

allocate customers.

…or advise others on their business decisions, and do not discuss yours (except

to the extent that they are already public).

…for advice from your own legal department, if you have questions about any

aspect of these guidelines or about a particular situation or activity at EPRI; or

ask the responsible EPRI manager to contact EPRI’s Legal Department.

DO NOT AGREE WITH

OTHERS

DO NOT TRY TO

INFLUENCE

ASK


Emergency Exits: Roosevelt BR (Mezzanine Level)

NOTE: ALL

RED DOORSARE EMERGENCY

EXIT DOORS

ROOSEVELT BALLROOM


Emergency Exits: Crescent City BR (Mezzanine Level)

NOTE: ALL

RED DOORSARE EMERGENCY

EXIT DOORS

Crescent City Ballroom

(Lunch Location)


Chemistry and Radiation Safety Technical Advisory Meeting

Monday, August 29 - Room Location: Roosevelt BR - Salon 5 (ML)

Time Topic Lead

8:00 am Welcoming Remarks and Introductions J. Goldstein, Entergy

8:05 am

Chemistry and Radiation Safety Program Overview

• The main purpose of this meeting is to discuss the 2017-2018

Program Plans

L. Edwards, EPRI

8:30 am

Program Showcase Projects

• Lithium-7/KOH Update

D. Wells, EPRI

J. McElrath, EPR

K. Fruzzetti, EPRI

9:30 am Chemistry Program for 2017-2018 D. Wells, EPRI

10:00 am Break

10:30 am Chemistry Program for 2017-2018 (continued)

D. Wells, EPRI

S. Choi, EPRI

K. Fruzzetti, EPRI

S. Garcia, EPRI

C. Gregorich, EPRI

N. Lynch, EPRI

J. McElrath, EPRI

12:00 pm Lunch – Crescent City Ballroom (Mezzanine Level)


Chemistry and Radiation Safety Technical Advisory Committee Meeting

Monday, August 29 - Room Location: Roosevelt BR - Salon 5 (ML)

Time Topic Lead

1:00 pm Chemistry Program for 2016-2017 (continued)

2:00 pm INPO Chemistry J. Sears, INPO

2:30 pm Methanol C. Cooney, Exelon

3:00 pm Break

3:30 pm Round Table (OE) ALL

4:30 pm EPRI Groundwater Resource Center Update B. Hensel, EPRI

5:00 pm Adjourn

5:30 pm Welcome Reception – Roosevelt Promenade & Foyer ALL


Lisa Edwards

Senior Program Manager

Chemistry and Radiation Safety

Technical Advisory Committee Meeting

August 29 -30, 2016

Program Overview Chemistry and Radiation

Safety

08/04/2016


Together…Shaping the Future of Electricity

EPRI’s Mission

Advancing safe, reliable,

affordable and environmentally

responsible electricity for society

through global collaboration,

thought leadership and science

& technology innovation

Independent, Collaborative, Nonprofit


Chemistry & Radiation Safety Technical Advisory Committee (TAC)

January/February: Technical Meeting

• Review Results of Previous Year’s Work

August/September: Business Meeting

• Review and Finalize Upcoming 2 Year Portfolio

• Make Recommendations to APC for Final Funding

Jeff Goldstein and Willie Harris will provide the TAC report to the Chemistry & Radiation

Safety APC on Wednesday morning

TAC Leadership (2016-2018)

TAC Chair: Jeff Goldstein, Entergy

Past Chair: Miguel Azar, Exelon

Vice-Chair: Willie Harris, Exelon

Meeting Objectives

APC Chair: Dennis Koehl, STP transitioning to Tim Powell in January

APC Vice- Chair: XXX

Senior Technical Advisor: Larry Haynes, Duke


Advisor Role Engage in TAC and APC meetings

– Give feedback on presentations

– Bring forward examples of how the work impacts you

– Take the information home

Act as a Tech Transfer Agent at Your Plant/Utility

– Know how to navigate the cockpit

– Find relevant reports

– Assist fellow employees with familiarization with EPRI research and products

Engage in Project Development & Demonstrations

– Submit project ideas

– Provide a prioritization input that represents your utility’s interests

– Provide input on project tasks and objectives

– Identify opportunities for your utility to engage with EPRI projects & committees

– Assist with data collection and submission


Randy StarkDirector

Fuel & Chemistry

Donald Cool

Carola Gregorich

Karen Kim

Rich McGrath

Sam Choi

Susan Garcia

Nicole Lynch

Joel McElrath

Dan WellsProgram Manager

Chemistry Program

Chemistry, Radiation Safety & Used Fuel Management

Keith FruzzettiTechnical Executive

Rick ReidProgram Manager

Used Fuel Management Program

Hatice Akkurt

Shannon Chu

Keith Waldrop

Phung TranProgram Manager

Radiation Safety Program,

Decommissioning

Lisa EdwardsSr. Program Manager

Chemistry, Radiation Safety & Used Fuel

Management

Paul FrattiniTechnical Executive

Colleen DasherAdministrative Assistant

Albert MachielsSr. Technical Executive

Kathy Danich

Project Operations Manager


Member Satisfaction Survey


2015 Nuclear Member Satisfaction Scores, By Area

≤86% 87%-90% ≥91%

Program AreaSurveyed

Co's

%

Response

Overall

Performance

Technical

Program

Value

Ease of

Doing

Business

Overall

SatisfactionTotal

Nuclear Sector Council 19/39 48.7% 94.4% 96.6% 81.1% 93.3% 91.3%

Materials Degradation / Aging 18/40 45.0% 91.5% 92.1% 84.2% 92.1% 90.0%

Fuel Reliability 15/40 37.5% 89.5% 91.4% 89.5% 89.5% 90.0%

Used Fuel and High-Level Waste

Management16/40 40.0% 96.8% 96.0% 90.5% 97.8% 95.3%

Nondestructive Evaluation 13/40 32.5% 90.0% 92.7% 81.8% 90.0% 88.6%

Equipment Reliability 30/40 75.0% 91.0% 91.2% 83.8% 90.7% 89.2%

Risk and Safety Management 16/40 40.0% 92.2% 94.4% 91.1% 91.1% 92.2%

Strategic Initiatives (ANT and LTO) 20/40 50.0% 95.0% 95.7% 90.7% 95.7% 94.2%

Chemistry and Radiation

Safety15/40 37.5% 94.4% 94.4% 88.8% 95.8% 93.3%

Total 92.3% 93.2% 86.1% 92.4% 91.0%


Current Improvement Actions (Program)

Member Satisfaction – Chemistry & Radiation Safety ProgramFocus on Continuous Improvement

Program Results: 2014 2015

99%Overall Performance

Ease of Doing Business

Technical Program Value

Overall Satisfaction With EPRI

95%

94%

94%

88%

• Research/ Standardize Project Prioritization

• Research Focus Areas –• Added step to prioritization process to

request project ideas from members • Business case included where applicable• Executive Summary – quick reference for

key take-aways, target audience, where in the document to find critical information

• Emails sent when new reports are released• ADD: Quality Management Program• ADD: Target Cost Saving Projects

• Training

• New Advisor training every NPC• Include discussion of advisor roles in TAC• Develop overview of EPRI, place on

cockpit• Training RFA had very low prioritization

• Cockpits

• Feedback to sector level on search engine• Hands-on tour through the program

cockpits in August

99% 96%

98%

2015 Member Feedback (Program)• Members want products that are:

• Timely, detailed, and of high quality• Relevant to plant operation• Positive economic impact• Easily implementable

• Training:

• For new advisors• On how EPRI works & how to work with the

program

• Website/Cockpits:

• Easier Access• State-of-the-Art Search Engine


Executive Summary Implementation

Objectives

Facilitate knowledge transfer

Get results to right people more quickly

Succinct

Consistent EPRI branding

Key Features

Consistent format and content

Key findings!

Directs readers to pertinent areas within the report

DOES NOT replace the Abstract, which is public facing Incorporated into deliverable templates and a stand-alone document

Important for Technology Transfer and Engagement!


Chemistry & Radiation Safety Base Funding

Expect base funding to be flat

for 2017 & 2018

– Includes special funds for

decommissioning

– $ for CWUG are included in

base funding for 2017 & 2018

Supplemental programs

enhance R&D scope

Future funding may change

from current $-

$0.500

$1.000

$1.500

$2.000

$2.500

$3.000

$3.500

$4.000

$4.500

2016 2017 2018

Fu

nd

ing

($M

)

Year

Chemistry and Radiation Safety Funding

Chemistry Base Radiation Safety Base Decommisioning Base


$-

$2.000

$4.000

$6.000

$8.000

$10.000

$12.000

2016 2017 2018

Fu

nd

ing

($M

)

Year

Chemistry and Radiation Safety Funding

Chemistry Base Radiation Safety Base

Decommisioning Base Decommissioning Supplemental

Technical Strategy Groups Leveraged

Supplemental Program Funders Technology Innovation

Strategic Gap Funds

Chemistry & Radiation Safety Overall Funding

Significant impact to research

portfolio due to

– Decommissioning

– Technical Strategy Groups

– Leveraged

– Program

– Technology Innovation

– Strategic Gap Funds


enhance R&D scope

Future funding may change

from current


Program Showcase

Li-7/KOH


Backup Slides


NPC/EC

Action Plan

Committee

Technical

Advisory

Committee

Users

Groups

Nuclear Power

CouncilExecutive

Committee

Chemistry & Radiation

Safety

Chemistry & Radiation

Safety

Technical

Strategy Groups

Decommissioning

Low Level

WasteRadiation Mgmt

& Source TermGroundwater PWR Chemistry

SMART ChemWorksTMChemWorksTM

BWR Chemistry

Programs

Base

Su

pp

lem

en

tal

Used Fuel Management

Used Fuel Management

Cask Loader


Dan Wells, Program Manager, Chemistry

Keith Fruzzetti, Technical Executive

Joel McElrath, Principal Technical Leader

Chemistry and Radiation Safety TAC Meeting

29-30 August 2016

Li-7 Usage, Supply,

Recovery and

Alternatives (KOH)Status Update

Submitted 19 July 2016


Li-7 for PWR Primary pH ControlPart 1: The Driver

Supports all three goals of PWR Primary Guidelines: materials, fuel reliability and radiation fields

Use of natural abundance LiOH would greatly increase tritium production

Reduces general corrosion

• Fuel crud and radiation field source term

Increases iron solubility across

the core

Stabilizes fuel crud:

• Core cruddingissues occurred in cycles with lower pH (≤6.9)

Impacts PWSCC initiation

• Minor factor

PWR Primary Water Chemistry Guidelines, Rev. 7 (2014). 3002000505. and PWR Fuel Cladding Corrosion and Crud Guidelines, Rev. 1 (2014). 3002002795.


Source: IAEA PRIS Database. Updated 29 Sept 2015

Li-7 for PWR Primary pH ControlPart 2: The Threat, Li-7 Supply

Some utilities were challenged to

procure Li-7 in 2015

– Production now back up in China and

Russia

– Supply is back, but at increased price

– Dependability of current supply routes

unknown

Operational considerations

– Flex power ops GREATLY

increases Li-7 demand

Growing PWR fleet

Molten salt reactors would

greatly increase demand

GAO-13-716, “Managing Critical Isotopes: Stewardship of Lithium-7 Is Needed to

Ensure a Stable Supply”, Sep. 2013.

Press Release, House Committee on Science, Space, & Technology, “GAO Raises

Questions about Adequate Supply of Lithium-7 for Nuclear Power Reactors”, Oct 9,

2013.


Two Paths to Maintaining pH Control Capabilities

Stay with Li-7 Qualify KOH

Optimized

UsageLi-7

Recovery

Alternative

Enrichment

Processes

Stockpile

How long would stockpiles last, if usage is optimized? Is FULL qualification necessary if there is no supply?

Higher upfront research costs, Lower operational costsLower upfront research costs, Higher operational costs

Materials

Chemistry

Control

Fuels

Radiation

Safety


Staying with Li for pH Control


Optimized

UsageLi-7

Recovery

Alternative

Enrichment

Processes

Stockpile



Materials

Chemistry

Control

Fuels

Radiation

Safety


Optimized Lithium Addition on Plant Startup

PWR Chemistry TSG


Optimized Li Usage - Main Takeaways

The later lithium is added to the RCS

during startup, the less total lithium

that should be required

Potential savings is between 10-20%

3002008184

June, 2016


Reported PWR Startup Lithium Usage

Large variation, with the average 12 kg added on start-up


Dilution Model Application

Used the model to compare different startup lithium addition

methods

Model was incorporated into an example PWR startup

dilution scheme

The later you add lithium in the startup process, generally

the more lithium you save

Savings, when looking solely at lithium adds between mode

2 through full power xenon-equilibrium, is 0.5 to 2.0 kg 7LiOH·H2O


Lithium Addition RecommendationsPractices plants can follow to limit lithium usage on startup

• Secure residual heat removal system prior to adding lithium

• Secure de-lithiating demineralizers prior to lithium additions

• Consider not flushing de-lithiating demineralizers to boron equilibrium

• Work with Reactor Engineering to obtain key parameters from the startup reactivity plan (e.g. critical boron, predicted boron/dilution trends on startup, and full power xenon-eq boron)

• Perform Li adds after reaching normal operating temperature/pressure, and just prior to diluting to criticality

• Maintain awareness of plant issues that may cause extended unit power holds, de-rates, or return to lower modes

• Just prior to xenon-eq, work with Operations to perform lithium additions to ensure pHT is increased to 7.0. Further lithium additions should occur within 24 hours of reaching xenon-equilibrium.


Lithium Addition RecommendationsPractices plants can follow to limit lithium usage on startup

• Secure residual heat removal prior to adding lithium

• Secure de-lithiating demineralizers prior to lithium additions

• Consider not flushing de-lithiating demineralizers to boron equilibrium

• Work with Reactor Engineering to obtain key parameters from the startup reactivity plan (e.g. critical boron, predicted boron/dilution trends on startup, and full power xenon-eq boron)

• Perform Li adds after reaching normal operating temperature/pressure, and just prior to diluting to criticality

• Maintain awareness of plant issues that may cause extended unit power holds, de-rates, or return to lower modes

• Just prior to xenon-eq, work with Operations to perform lithium additions to ensure pHT is increased to 7.0. Further lithium additions should occur within 24 hours of reaching xenon-equilibrium.


Lithium Recovery Project

STATUS

Non-radioactive testing has been

completed

– Two viable methods for recovering lithium

– Lithium recovery exceeds 90%

– Recovered Li purity is high (99.9% Li)

– Draft report under EPRI review

Radioactive testing

– Commenced in August, 2016

– Waste resin provided by

Diablo Canyon

2016-2017 SCHEDULE

Radioactive resin testing

Complete engineering design of

demonstration

Perform lab-scale demonstration


Lithium Recovery ProjectRadioactive Media Testing

Laboratory testing of actual CVCS spent resin from Diablo

Canyon

– Started at Westinghouse facilities in August

– Prove the viability of recovering lithium-7 from CVCS resin

– Determine to what extent are radioactive isotopes eluted along with

the lithium

– Identify if there is an optimal point where lithium recovery is

balanced against radioisotope elution


Stockpiles

US Department of Energy (DOE)– 500 kg as LiOH

Partially purified

– Approximately enough for 28 PWR operating cycles (does not include that necessary for CVCS bed lithiation)

– Contains 3100 ppm SO4

DOE understands this is unacceptable

DOE is considering means for purification

– NEI will prepare process for dissemination

Utility Stockpiles– May provide some flexibility in supply

– Cost approaching $2,500/kg


Alternative Enrichment Processes

Colex

– Mercury-based

– Environmental regulations prohibit this process in most countries

Atomic Vapor Laser Isotope Separation (AVLIS)

– Laser separation

– Performed for several other elemental isotopes, but not yet ready

for large scale applications

Crown-Ether

– DOE has proposed work


Current Industry Activities – EPRI Li-7 Strategy

Funding – DOE/EPRI Match

EPRI technology under development

3rd party commercializer needed

1-3 years estimated to commercialize

Reduce cycle usage (TSG Project)

Enriched Boric Acid usage

What is the impact of flexible ops?

Utility specific stockpiles

DOE stockpile (significant but needs

additional purification, sulfate contamination)

Colex & NCCP – mercury based

AVLIS

Crown-ether (DOE work)

Optimized Usage

Lithium (Waste) Recovery

Stockpile

Alternative Enrichment Processes

EPRI

EPRI

Utility

DOE

Nat. Labs

Vendor


Qualifying KOH for pH Control


Optimized

UsageLi-7

Recovery

Alternative

Enrichment

Processes

Stockpile



Materials

Chemistry

Control

Fuels

Radiation

Safety


Potassium Hydroxide (KOH): Motivation

ELIMINATE the Significant Vulnerability of Li-7 Supply

Approximately 26,500 kg LiOH•H2O / yr / unit needed*

(Estimated average yearly use for a PWR: 35 kg**)

Molten Salt Reactor (LiF – BeF2 – ThF4 – UF4)

* Based on information from: Engel, J.R. et al., “Molten-Salt Reactors for Efficient Nuclear Fuel

Utilization Without Plutonium Separation”, ORNL/TM-6413, Aug 1978. Basis: 1000 MWe.

** Includes lithium required to saturate a CVCS resin bed

(72% – 16% – 12% – 0.4%)

Eliminate dependence on Li-7

supply

– Existing supply chain vulnerability

– Growing worldwide PWR fleet

– A single Molten Salt Reactor

(1000 MWe) requires as much

Li as 760 commercial PWR units


Additional Benefits of KOH

Lower Operational Costs

– LiOH•H2O: Approximately $2,500/kg

– KOH: Approximately $25/kg (Reagent Grade)

– Standard vs Lithium saturated CVCS bed (approx. $300 vs $6000 per ft3)

– Estimated savings per yearEach PWR unit: $140kU.S. Fleet (65 PWR units): $9.1M

May be more beneficial for Fuel

– Data indicates much lower corrosion rates

May mitigate IASCC* initiation (e.g. baffle-former bolts)

– Much lower lithium concentrations possible with KOH

*IASCC: Irradiation Assisted Stress Corrosion Cracking

10

100

1000

10000

1 10 100 1000 10000 100000

Co

rro

sio

n R

ate

(mg/

dm

2)

Concentration of Cations (ppm)

Zircaloy 2

NaOH

LiOH

KOH

Co

rro

sio

n R

ate

(m

g/d

m2)

Corrosion Rate of

Zircaloy 2 at 360°C

Concentration of Cation (ppm)

H. Coriou, L. Grall, J. Neunier, M.

Pelras, and H. Willermoz, “The

Corrosion of Zircaloy in Various

Alkaline Media at High Temperature”,

Corrosion of Reactor Materials, Vol. II,

193, IAEA, Vienna (1962).

NaOH

LiOH

KOH


Feasibility of KOH vs LiOH for PWR Primary pH ControlPublished October 2015 (3002005408) – Reference/Early R&D

VVER Operating Experience

– Successful use of KOH for

over 40 years

– Generally low corrosion and

very low radiation fields

– No observed Crud Induced

Power Shift (CIPS)

Materials

• Initiation and CGR of austenitic stainless steel and nickel based alloys

Fuels

• Corrosion and hydriding of zirconium fuel cladding – with crud and boiling

Chemistry

• Management of Li and K for pHT control

• High temperature chemistry

Radiation Safety & Radwaste

• Radiation Fields

• Dose pathways

• Waste classification

• Effluents

Appears very promising. Some next steps underway. Detailed multi-year plan developed.

Key Gaps

Important differences between VVER and Western-PWRs

– Materials: Titanium-stabilized SS (VVER) vs nickel-based alloys (PWR)

– Fuel cladding: Both zirconium alloy (KOH less corrosive), but low crud

and lower boiling (VVER)

– Chemistry: Ammonia for hydrogen (VVER) vs dissolved hydrogen gas

(PWR), Li/K new to PWRs

– Worker dose & Radwaste: Potassium activation products (VVER)


Chemistry and RS Challenges

Boric acid concentration, g/l

Pota

ssiu

m c

oncentr

atio

n,

ppm

Lith

ium

co

nce

ntr

atio

n,

pp

m

0.6

43210

18

16

14

12

10

8

6

4

2

0

0.5

0.4

0.3

0.2

0.1

0

65

Potassium

Lithium

Potassium Hydroxide: A Potential Mitigation for AOA. EPRI, Palo Alto, CA: 1999. TE 114158.

• Control of Multiple Alkali

• Li and K

• New activation species

• 42K, 40K, etc…

Adds Complexity to pHT Control: Now Li and K. New activation species to manage.


Detailed Plan for Qualifying KOH Developed (Summary)

Fuel Vendor Assessment

Experimental Loop Testing

Fuel Exams

Crack Initiation & Crack Growth Rate Testing

–Non-irradiated testing

Stainless Steel and Alloy 600

–Irradiated testing

Stainless Steel

Activation species and dose pathways

Effect on plant radiation fields

Effluent and radioactive waste handling

High temperature chemistry (MULTEQ)

Purity specifications

Multiple alkali (Li & K) modeling and control

Materials Testing

Fuels Testing and Exams

Radiation Fields and Radwaste

Chemistry / pH Control

MPR

FRP

RS

Chem


Full Qualification Plan – Shortest Timeline

“Plan A” (Reasonably Conservative)• Detailed project scopes developed for each technical item• 8 – 10 years• $8M - $10M

What is truly

necessary in the

face of no Li

availability?

“Plan B”

Phase 1: Qualification ahead of the PWR plant trial

Phase 2: PWR plant trial

Start of Phase 2


Qualification Plan – Next Step: Investigate a “Plan B”

Can we eliminate CGR Testing?

Can we reduce the time/scope of initiation testing?

Motivation/Scenario

• All Li-7 supply is gone.

• Operate plant with

alternate pH control

chemistry, or shutdown.

• What is the absolute

minimum to have been

completed to allow

operation with KOH?

“Plan B” Effort

• Work directly with a

utility willing to consider

this premise.

• Include 3 – 5 utility

experts

• Requires executive

level input.

Can we eliminate these evaluations from the qualification

process, and simply evaluate as part of the trial application?

Work with fuel vendors to define acceptable risks


Discussion Questions: Where We Need Help

Are you seeing changes in Li-7 price?

How long will stockpiles last?

When should work on Plan A start?– Program funding not likely till 2019 (MRP) or 2018 (FRP)

– This need executive support either way

What does the emergency KOH plan “B” look like?– Any volunteers to support development?


Dan Wells, Program Manager, Chemistry

Sam Choi, Keith Fruzzetti, Susan Garcia, Carola Gregorich and Joel McElrath

Chemistry and Radiation Safety TAC Meeting29-30 August 2016

Water Chemistry Program2017-2018 Work Plan

Submitted 10 August 2016, Rev. 2


2017 – 2018 Water Chemistry Control Budget

No change to base

funding

Significant amount of

leveraged funding

– Greater than base funding

(includes RS co-funding)


enhance R&D scope

$-

$1.0

$2.0

$3.0

$4.0

$5.0

$6.0

2017 2018

Fundin

g (

$M

)

Year

Chemistry Base Chemistry Program Members

Leveraged Funding Technical Strategy Groups

Smart ChemWorks Users Group


Chemistry Research Focus Areas

Chemistry Guidance (Guidelines, Sourcebooks)

Management of Corrosion Product Behavior and Impacts

Chemical MitigationRadioactivity Generation and Control (Source Term Reduction)

Chemistry Monitoring and Control

Joint with RS

Chemistry Modeling(Fundamental)

Chemistry Benchmarking and Trending (Fundamental)

Fundamental RFAs – Not Prioritized

RS = Radiation Safety Program


2017-2018 Water Chemistry Recommended Portfolio

Chemistry Guidance (Guidelines,

Sourcebooks)

PWR Secondary Chemistry Guidelines Revision 8

(2015-2017)

Revision to the Condensate Polishing Guidelines

(2016-2018)

BWR Water Chemistry Guidelines Rev. 8

(2018-2019)*

Open Cooling Water Guidelines Review (2017)*

Risk Informed Chemistry Control (2017-2018)*

Chemical Mitigation

Effect of Amine Decomposition Products on

Crack Growth Rates (2017-2019)*

Hydrazine Alternatives (2018-2019)*

Qualification of KOH for Plant Trial (2017)*

High-Concentration Dispersant Corrosion Testing

Management of Corrosion Product

Deposition and Transport

PWR Secondary Side Filming Amine (FA)

Application (2016-2017)

Dispersants: SG Deposit Evaluation (2017-2018)*

Filming Amine Qualification Testing (2018-2019)*

Impact of Fuel Materials Changes (2018-2019)*

Gap Assessment of Boric Acid and Silica

PWR Primary Crud Reaction Kinetics

Dispersants Beyond Secondary

Radioactivity Generation and

Control (Source Term Reduction)

Micro-Environment Effects(2015-2017)

Surface Passivation of Primary Components

(2015-2018)

Hydrophobic Coatings for Contamination Control in

NPP (2016-2017)

Behavior of Ag and Sb(2016-2018)

Optimization of Zinc for Benefits and Cost

(2018-2019)*

Impact of BWR Ultra-low Iron and Reducing Conditions


On-Line Monitoring of Anions (2016-2017)

On-Line Iron Analysis (2018)*

High Efficiency Purification Media

X-ray Fluorescence Analysis

Plant Experience with CoSeq®

Improve Quantification of Cobalt

Mean = 1.5 Mean = 1.7Mean = 1.7 Mean = 1.9 Mean = 2.0

Funded Work Unfunded Fund with Modification *new


2017-2018 Prioritization Feedback BreakdownWater Chemistry Program

40 of 49 Respondents

(82%)

US or Non-US

US20 of 23 (87%)

Non-US20 of 26 (77%)

By Plant Type

PWR (PWR, PHWR, VVER) 23 of 26 (92%)

BWR7 of 10 (88%)

Both10 of 13 (77%)

59 Comments


Incorporating Feedback and Industry Objectives into Portfolio

• Continues to be highest priority RFA

• Recommend to fund “Risk Informed Chemistry Control” Project


• Significant change in priority; now high

• Fund highest priority work to balance with other objectives

Chemical Mitigation

• Consistently high priority

• Continue high priority technology evaluations

• Co-fund fuel materials project with RS

Management of Corrosion Product Deposition and Transport

• Significant change in priority from previous year

• Recommend reduction in scope where possible

Radioactivity Generation and Control (Source Term Reduction)

• Medium priority

• Opportunity to support utilities in DNP objectives

• Only fund online monitoring work


A significant shift in RFA priorities– Mainly reduced priority on

Source Term Reduction work

Aiding the industry in Delivering the Nuclear Promise– Opportunities for cost

saving technology from Chemistry are likely associated with sampling and analysis

Risk informed control

Online monitoring


Proposed Base Program Funding Breakdown By RFA

Proposing a gradual transition away from previous prioritization to new prioritization


2017 – 2018 Water Chemistry Budget and Funding Distribution

Funding of new projects based on completion of multi-year projects and current prioritization

Stable funding for long term, strategic projects

– Fundamentals

– Guidelines

– New and promising technologies


Recommended Water Chemistry Control

2017-2018 Portfolio

by Research Focus Areas


R&D Research Focus Areas




Sourcebooks)


(2015-2017)


(2016-2018)


(2018-2019)*



Chemical Mitigation





High-Concentration Dispersant Corrosion

Testing







Impact of Fuel Materials Changes

(2018-2019)*








(2015-2018)


NPP (2016-2017)



(2018-2019)*

Impact of BWR Ultra-low Iron and Reducing

Conditions


On-Line Monitoring of Anions

(2016-2017)








Chemistry Research Focus Area:


Development of practical guidance and sound chemistry control guidelines represents the culmination of EPRI’s research and development efforts in water chemistry control

Maintain our suite of mature guidelines and sourcebooks

Near term efforts will focus on review and revision to several guidelines and analysis of applicability to current industry operating status (shutdowns prior to license end, flexible operations, new designs)

Long term efforts will include expanding applicability beyond BWRs and PWRs

Project types

Guideline

Development

Sourcebook

Development


Highest Priority Chemistry Research Focus Area:


Summary of Qualitative Member Feedback

– “Required guideline projects drive this rating”

– “Need guidance for flexible operations”

– End of plant life chemistry project: “…the decision to perform a

D&D or LTO can change very quickly and also depends on

governmental decisions.”

– “I like the project for the plants shutting down as they have no

guidance now”

– “Should cut End of Plant Life Chemistry and Condensate

Polishing Sourcebook.”

Proposed Scope Adjustments

– Extend Revision of Condensate Polishing Guidelines to 3 years

(originally schedule to complete in 2017)

Utility lead for revision has agreed

– Expand and revise End of Life Chemistry Control proposal –

new Risk Informed Chemistry Control

Leveraged Funding

2017: $10K

2018: $160K

Median = 1.5



Condensate Polishing Sourcebook RevisionPriority Issues from February Revision Committee Meeting

New amines and OE related to amine fouling

Use of CPs for only plant start-up

New media, including macroporous and orthoporous resins

New media retention element designs and fabrication

Improved methods and practices

Experience with filter demineralizer resin traps for CP

applications

Improving backwash effectiveness with air-surge backwash

systems

Current industry practices relative to body feed

Recent OE with upgrades to instrumentation and controls for

filter demineralizer systems

Best practices for chemistry monitoring of CP systems

Value Statement

Prepare a revision of the Condensate

Polishing Guidelines that incorporates

the most recent developments in

operating experience and related

technologies.

Proposed Duration and Timing: 2016 - 18 (32 mo.)


Condensate Polishing Sourcebook RevisionChange to Revision Schedule

3rd Qtr ‘16: Webcast- Review approach to issues

3rd Qtr ‘17: Meeting #2 - Review draft resolution

4th Qtr ‘17: Issue draft to Revision Committee

1st Qtr ‘18: Webcast - Review draft

3rd Qtr ‘18: Publish Condensate Polishing SB

Industry Lead: Michelle Mura, Exelon


Open Cooling Water Chemistry Guidelines Review

Description & Objectives

EPRI Guidelines issued 2012

(first edition)

Review meeting to evaluate:

– New technologies

– Operating experience

– How is the document being used?

– Are the performance measures

appropriate?

– Identify technical basis needs that may require further R&D

Are there any issues driving the need for revision?

J. McElrath


EPRI Chemistry Guidelines

applied world-wide

Used by both the Nuclear

and Generation (fossil) members

World-wide research results and operating

experience utilized for new and developing

guidance

Open Cooling Water Chemistry Guidelines Review

Industry-consensus document that is

developed and reviewed by:

– Nuclear members

– Fossil members

– Water treatment vendors

– Open cooling chemistry experts

Global Applicability

Proposed Duration and Timing: 2017 (8 mo.)

Prepare a revision of the Condensate Polishing

Guidelines that incorporates the most recent

developments in operating experience and

related technologies.

Value Statement


BWR Water Chemistry Guidelines Review/Revision


EPRI Guidelines (BWRVIP-190, Rev. 1) issued April 2014,

implementation Jan 2015

Drivers for initiating review and revision process

S. Garcia

Significant Interim Guidance to be issued in 2016

Mitigation Performance Indicators (MPIs)

•Revised due to issues with potential low oxidant levels in external monitoring system

Revised Action Level-1 values for reactor water chloride

•R&D results indicate concerns exist for low alloy steel in oxidizing environments

New guidance considerations

Extended lower power operation (Flexible Operations)

•Practiced by Columbia, Quad Cities, others soon…

Advanced BWR designs (ABWR and ESBWR)

•ABWRs have operated in Japan and are soon to be under construction in U.K.

Operating experiences

Application of methanol injection during startup at LaSalle in March 2016

Continued use of CoSeq® for enhanced cobalt removal/dose reduction

Experience with new online monitoring equipment (FW silica and RxW chloride and sulfate}

Time to

Revise the

Document


EPRI Chemistry Guidelines

applied world-wide

Required for U.S. BWRs

Non-U.S. BWRs utilize guidance for their own

regulatory requirements/operations

World-wide research results and operating

experience utilized for new and developing

guidance (Finland, Germany, Japan, Mexico,

Spain, Sweden, Switzerland, U.S.)

BWR Water Chemistry Guidelines Review/Revision

Industry-consensus document that is reviewed

and approved by multiple technical areas

(chemistry, fuel, materials, operations, radiation

protection)

Volume 1: All guidance (Mandatory, Needed,

Good Practice, Diagnostic Parameters)

Volume 2: Technical basis and excellent

go-to-source for training of new personnel


Proposed Duration and Timing: 2018-2019 (24 mo.)

Co-funding proposal will be made to BWRVIP


Risk Informed Water Chemistry ControlGuidance for Short Term Operation (STO) and Economic Constraints

Current water chemistry control guidance based on:– Base load, full power operation

– Long Term Operation (LTO)

What if operation for an additional 20 years isn’t an objective?– How should a plant operate if they know they will

shutdown in 2 years?

Could costs be reduced with alternate chemistry control under prerogative of STO or economic hardship?

What does guidance for Short Term Operation (STO) look like?

D. Wells


Objectives

– Provide a technical evaluation of chemistry control areas where risk and economics can be considered

– Support ‘Delivering the Nuclear Promise’ (DNP) initiatives through evaluation of flexibility in chemistry control

– Support plants that have changed from LTO to STO and want to manage cost going into decommissioning

Risk Informed Water Chemistry Control

Scope of Work

– Evaluate chemistry control guidance (technical basis) for potential modifications when risk, economics, and time till shutdown are considered

Chemistry holds, sampling frequency, analysis type, chemical additions, etc.

– Evaluate the impact of applying advanced analysis/sampling technologies

Evaluate the potential savings (and cost) associated of online monitoring technologies

What technologies (which analysis) will have the largest impact on plant economics

– Evaluate for plants heading to decommissioning

Can or should they sell equipment and consumables?

Can or should they run systems to empty

system shutting down…

STO = short term operation


Risk Informed Water Chemistry ControlConsideration of Cost Minimization and Time till Shutdown

Careful, detailed evaluation of the risk

associated with not meeting current chemistry

control programs, systems, monitoring can

help utilities meet economic demands and

reduce cost

Industry Use and Schedule

PWR Chemistry TSG started work in 2015 on

evaluating sample frequency and potentials

for reduced frequencies – this will be

leveraged

2017 will focus on BWR in order to provide

input to Guideline revision starting in 2018

and current round of plant closures

Without a revision of PWR Primary or

Secondary, information could be used to

support any necessary Guideline deviations





Sourcebooks)


(2015-2017)


(2016-2018)


(2018-2019)*



Chemical Mitigation






Testing








(2018-2019)*








(2015-2018)


NPP (2016-2017)



(2018-2019)*


Conditions



(2016-2017)









Chemical Mitigation Water chemistry control plays a substantial role in material

degradation modes such as environmentally assisted cracking (IGSCC, PWSCC, PbSCC, ODSCC, Li-enhanced cladding and nickel-based alloy corrosion, etc.)

Past work has included:– HWC, NMCA/OLNC, DZO and Cu controls for BWRs;

– Zn application and H2 optimization in PWR primary coolant;

– SG chemical cleaning, advanced amines, and control of Pb and Cu in PWR secondary systems

– Li-borate speciation to understand Li-enhanced fuel cladding corrosion

Near term work will focus on oxygen control using alternatives to hydrazine, understanding the impact of amine decomposition products, and application of KOH for pH control in PWRs

Project types

Development of new

chemical mitigation

control technologies

Understanding the

fundamental

mechanism of

chemically assisted

degradation

Impact of chemical

mitigation techniques

on plant safety and

operability


Second Highest Priority Chemistry Research Focus Area:

Chemical Mitigation


– “Steam turbine research/guidance is important to the PWR industry.”

– “Why do a high conc PAA Carbon Steel study…use it diluted and save the money.”

– “The hydrazine replacement project is highly relevant to European [and COG] operators given the potential impact of the REACH legislation on use of hydrazine.”

– “The KOH program should be prioritized as the threat of Li supply shortages has not fully dissipated and for our company…this is a real challenge.” – 4 total positive comments, 1 negative


– Set aside small amount of funds to evaluate “Emergency KOH Use” tasks – those operational topics that would be necessary even if the utility decides to operate at risk with KOH – revisit 2018+ funding next year.

2017

$170K leveraged funds

2018

$210K leverage funds


Median = 1.7


Effect of Amine Decomposition Products on Steam Turbine MaterialsCrack Growth Rate Testing (Steam Chemistry Phase 2)

Background & Objectives

PWRs use amines for secondary chemistry control to reduce FAC and corrosion product transport

to the steam generators (SGs)

The challenge is achieving both the needed chemistry for the balance of plant and the SGs, and

the needed chemistry for the steam turbines; specifically use of amines

– Difficult to achieve both proper secondary water chemistry and currently allowable steam cation

conductivity for the steam turbine

– Gap: Are amine degradation products (e.g., acetate and formate) detrimental to turbine materials?

– Warranties may be affected

– EPRI cooperating with steam turbine vendors to develop appropriate technical basis and guidance:

Phase 1: Pitting Testing (currently underway)

Phase 2: Crack Growth Rate Testing (this project)

Objective: Address steam turbine warranty issue caused by amine addition for pH control

Collaborative with SGMP

and Fossil Chemistry

K. Fruzzetti


Effect of Amine Decomposition Products on Steam Turbine MaterialsCrack Growth Rate Testing (Steam Chemistry Phase 2)

Scope

Task 1: Development of the Test Plan and Procedure

– Develop the test program as informed by the Phase 1 testing (Pitting Testing)

Fatigue crack growth rate measurements per ASTM E647 in air, in a control water chemistry, and in water chemistries with appropriate concentrations of acetate and/or formate

Task 2: Procure turbine materials for testing and fabricate test materials

– Mechanical specifications will be more important than in pitting testing, coordinate very closely with turbine vendors

Task 3: Perform the testing and evaluation

– Anticipate eight materials will be tested in three environments each (air, control chemistry, and control chemistry with acetate and formate)

One temperature

Duplicate selected tests to ensure robust test data and associated analyses


Value: Develop technical basis supporting amine application while also protecting the turbines


KOH Qualification Plan – Next Step: Investigate a “Plan B”

Can we eliminate CGR Testing?

Can we reduce the time/scope of initiation testing?

Motivation/Scenario

• All Li-7 supply is gone.

• Operate plant with

alternate pH control

chemistry, or shutdown.

• What is the absolute

minimum to have been

completed to allow

operation with KOH?

“Plan B” Effort

• Work directly with a

utility willing to consider

this premise.

• Include 3 – 5 utility

experts

• Requires executive

level input.

Can we eliminate these evaluations from the qualification

process, and simply evaluate as part of the trial application?

Work with fuel vendors to define acceptable risks

K. Fruzzetti


Hydrazine AlternativeA Comprehensive Evaluation – Field Trial

Description & Issue

– There is a long history of use of hydrazine as a

feedwater chemistry additive (oxygen

scavenger and pH control agent) at both PWRs

and fossil power plants.

– While hydrazine is effective, it is toxic and a

suspected carcinogen.

– Alternatives to hydrazine are desirable due to

the personnel safety and environmental issues

associated with hydrazine

Especially important for countries meeting

REACH requirements (Europe and Canada,

others)

Overall Project Objectives

– Identify and qualify an alternative to hydrazine

for PWR primary and secondary side

application

Overall Project Scope

– Literature review (2016-2017 PWR TSG)

– Laboratory testing at SG wet layup conditions*

(2016-2017 PWR TSG)

– Field Trial and Data Assessment

(this project)

S. Choi


Applicable for global PWRs and fossil

units

Potential collaborative effort with EdF

and ENGIE being evaluated

Hydrazine AlternativeA Comprehensive Evaluation – Field Trial

Provide valuable information in

determining whether a hydrazine

alternative can be acceptable for

general use in the primary and

secondary systems of PWRs






Sourcebooks)


(2015-2017)


(2016-2018)


(2018-2019)*



Chemical Mitigation






Testing








(2018-2019)*








(2015-2018)


NPP (2016-2017)



(2018-2019)*


Conditions



(2016-2017)







Co-funded with RS,

Discussed in RS slides




Includes all efforts to understand corrosion product behavior; to control the generation, transport and deposition of corrosion products; and to mitigate the effects of corrosion products in plant systems – focused on non-radiation field related species (bulk species)

Near term efforts focus on control of corrosion products affecting PWR primary and secondary system performance and integrity

Long term potential efforts – Auxiliary systems

Project types

Mitigation of corrosion

product generation and

deposition

Basic R&D to

understand corrosion

product formation,

transport and

deposition

Corrosion product

removal techniques


Corrosion Product Mitigation Technologies

Fe2+

Filming Amine (FA) Technology

N

H HCH

N

H HCH

N

H HCH

N

H HCH

N

H HCH

N

H HCH

N

H HCH

N

H HCH

N

H HCH

N

H HCH

N

H HCH

N

H HCH

Full Secondary System

H2O

loosely adherent Fe deposits

Dispersant (PAA) Technology

SGBalance of Plant

FexOy

Base Metal

CS, SS, Ni-based alloys

coolant Fe2+X

FexOy


Third Highest Priority Chemistry Research Focus Area:



– Filming Amine “…is a perspective method for corrosion

product management and will benefit for the long term

preservation of assets.”

– “The interaction of B and Silicates may only apply to a

smaller population of plants…“

– “Further research with silica should be performed to

provide some additional operating margin for plants with

Boraflex. An update to TR-107992 is needed.”

– “…some elevated interest in the Effects of Radiation on

Chemistry Kinetics during shutdown.”

– “Would not spend the money for PAA use beyond PWR

without Westinghouse/GE permission up front.”


– None

– Fund highest priority and collaborative scope

2017

$275K leveraged funds

2018

$285K leverage funds

Median = 1.7



Evaluation of Dispersant Impacts on Steam Generator Tube Deposits

Background & Objective

Issue

– Significant benefit in reducing SG fouling rate, but effect

on plant-specific SG thermal performance is not well

understood.

Action

– A careful assessment of SG deposit characteristics,

deposit spatial profiles, and cumulative PAA exposure

Goals

– Confirmatory evidence that interactions between PAA and

SG tube deposits lead to partial removal of SG deposits.

– Greater insight concerning the relationship between PAA

exposure and changes in deposit properties and SG

thermal performance trends.

– Added input to plant-specific SG deposit management

strategies. -40

-35

-30

-25

-20

-15

-10

-5

0

5

10

McGuire 2(LTT - 1 yr)

Byron 1(4.9 yrs)

Byron 2(3.7 yrs)

Braidwood 1(4.5 yrs)


STP 1(2.7 yrs)

STP 2(2.4 yrs)

Ginna(1.7 yrs)

Estim

ate

d P

AA

Effe

ct o

n S

G F

ou

ling

Fa

cto

r(µ

h-f

t2-F

/Btu

)

Max Change

Change as of Most Recent Data

(0) (0)(0)(0) (0)(0)

~ 4 psi

(28 kPa)

increase

~ 4 psi

(28 kPa)

decrease

~ 4 psi

(28 kPa)

increase

~ 1 psi

(7 kPa)

increase

< 1 psi

(< 7 kPa)

decrease

~ 1 psi

(7 kPa)

increase

Lower is

Better

K. Fruzzetti

0

5

10

15

20

25

30

35

40

45

McGuire 2(LTT - 1 yr)

Byron 1(4.8 yrs)

Byron 2(3.5 yrs)



STP 1(2.8 yrs)

STP 2(2.5 yrs)

Ginna(1.7 yrs)

Ste

ad

y S

tate

Blo

wd

ow

n I

ron

Re

mo

va

l Eff

icie

ncy

Before PAA

With Online PAA

Not

eval.

Blowdown Removal Efficiency

SG Fouling Factor Analysis

Higher is

Better


Evaluation of Dispersant Impacts on Steam Generator Tube Deposits

Project Approach

– Optical microscopy of tube scale samples to identify any changes in physical properties

that might be associated with PAA exposure

– Analysis of routinely collected low-frequency eddy-current signals (to evaluate any change in

SG tube deposit spatial distribution with PAA exposure)

– Calculations of the integrated PAA exposure (to understand impacts of time

and concentration)

– Quantification of the total blowdown iron oxide mass removals (to estimate

removal from SG tubes)


Approved for 2017 funding in 2016-2017 Portfolio

Value: Provide improved prediction of PAA impact on SG thermal

performance to guide plant-specific SG management strategies


PWR Filming Amine Qualification TestingFollow on to 2015-2017 Scoping and Plan Development


Filming amines have been applied at fossil plants for over 25

years as a means of protecting carbon and low alloy steel

components, especially during periods of long layup

Recently, a filming amine has been applied at the Almaraz

Nuclear Power Plant in Spain and tested at Embalse in Argentina

S. Choi

Condenser Hotwell Inspection

Condenser Hotwell (close-up view)

Phase 1: Scoping and Plan Development

•Funded project

•2015-2017

Phase 2: Qualification Testing

•Current Proposal

•2018-2019

Phase 3: Plant Demo

•Future proposal if promising

• Identify 3-5 candidate

materials*

• Develop qualification

program

*Collaborative license agreement with AREVA Gmbh


PWR Filming Amine Qualification Testing2018-2019 Project

Phase 2 Objectives

Complete technical tasks in preparation for conducting a plant trial to demonstration safe use of the FA on the PWR secondary system

Phase 2 Scope: Qualification Testing

Identify a (1) commercial FA for qualification testing and eventual plant trial

– Based on selection criteria: state of commercialization, existing qualification work, similarity to other molecules, etc.

Complete qualification testing

– Purity, Stability, Efficacy, Material Compatibility, Effects on Chemistry, Thermal Performance, Effects on Flow Measurement Device

Qualify a new technology, FAs, to aid in minimizing release, generation, and accumulation of corrosion products in PWR steam generators

Assist utilities for generation of a generic 50.59 safety evaluation


– Applicable for global PWRs and fossil units

– An active collaboration is under development with COG

– Working on potential collaboration from MAI


Approved co-funding with SGMP (2018) and Potential Generation being evaluated




Sourcebooks)


(2015-2017)


(2016-2018)


(2018-2019)*



Chemical Mitigation






Testing








(2018-2019)*








(2015-2018)


NPP (2016-2017)



(2018-2019)*


Conditions



(2016-2017)








Joint Water Chemistry and Radiation Safety Research Focus Area:

Radioactivity Generation and Control

Focused on minimizing and controlling the radioactivity (i.e. source term) that is generated from nuclear power plant operations

Addresses technologies and strategies for minimizing plant radiation fields

Near term efforts include evaluations of other radionuclides (e.g. non-cobalt) of potential importance to worker exposures, surface modification to minimize contamination and recontamination, optimization of current techniques, and impact of new operating chemistry

Project types

Literature

Reviews/Feasibility

Studies

Laboratory Testing

and Analysis

Plant Demonstrations


Fourth Highest Priority Water Chemistry RFA (Jointly Funded with Radiation Safety Program):

Radioactivity Generation and Control


– “Most interested in Optimization of Zinc Injection…”

– “Don't want to go too far and fund project to the point of diminishing returns.

– “I like the use of hydrophobic coatings as a way to reduce contamination.”

– “The micro-environments and silver/antimony projects are vital if we are to continue to deliver improvements in radiation fields…”

– “With the nuclear promise we need to take a hard look at all the source term related work…”

Proposed Adjustments

– Significant change in priority from 2015 (2016 Portfolio)

– Proposal to reduce Chemistry funding on this RFA

Combine scope of Micro-environments and Ag and Sb projects

RS safety (higher priority RFA) increases funding2017

$325k leveraged funds

2018

$320k leverage funds

Median = 1.9



Merging Micro-Environment and Silver/Antimony Projects

Radiation field effects of micro-environments result from surface interaction

of ionic, solvated, and activated species

– Species of emphasis originate from Zn, Ni,

Co, Cr, Ag, and Sb

– Speciation and surface interaction are

temperature and pH dependent

– Micro-environments of emphasis – low

temperature regions (RHR, clean-up,

heat exchangers)

Current radiation field challenges make

a merge a natural fit

– High Ag/Sb contribution in low temperature regions

with unclear Zn influence

C. Gregorich

Better Together


Ag/Sb/Zn – Low Temperature Speciation - Scope

2016

– Finalize OE review of micro-environments report

– Review state-of art knowledge on silver and antimony speciation under LWR

conditions

– Develop experimental program to investigate speciation and surface

interaction of silver, antimony, and zinc

2017

– Start experimental studies

2018

– Finalize experimental studies and report findings

Value – Builds Foundation for Modeling and Developing Mitigation Technologies__


Updated Evaluation of the Effect of Zinc

Background:

– EPRI published 1021111, “PWR Zinc Application: Data Analysis

and Evaluation of Primary Chemistry Responses” in 2010

– Since 2009, 30 additional PWRs have started zinc injection.

– The project will evaluate the new experiences along with changes in

practices such as:

Optimized injection programs

Varying experience with end-of-cycle injection termination

Purpose:

– The results of this project will refine the industries’ understanding of how

zinc affects primary system chemistry, and will allow optimization of zinc

programs to achieve maximum benefit with minimal risk.

J. McElrath


Updated Evaluation of the Effect of Zinc

Research Value:

This project will provide utilities with information to better optimize the zinc

injection regime and to better predict plant behavior when implementing and

continuing zinc injection (i.e., both long and short term), including:

– Estimating impact upon radiation fields

– Estimating impact upon PWSCC mitigation

– Assess concerns such as release of nickel, increased radiocobalt

concentrations, shutdown cobalt releases, etc.

– Assess potential causes for dose rates reduction outliers





Sourcebooks)


(2015-2017)


(2016-2018)


(2018-2019)*



Chemical Mitigation






Testing








(2018-2019)*








(2015-2018)


NPP (2016-2017)



(2018-2019)*


Conditions



(2016-2017)










Water chemistry control requires analytical techniques and protocols for effective monitoring and techniques to adjust and maintain water chemistry within optimum limits

Work in this Research Focus Area includes– Development of new or enhanced analytical

methods;

– New technologies for water treatment, including ion exchange resins, filtration media and other systems for maintaining water quality and reducing plant effluents

Project types

Analysis technique

evaluation and

development

Technologies for the

removal of detrimental

species


Lowest Ranked Chemistry Research Focus Area:



– “Online monitoring is becoming more important over

time due to manpower reductions and improved

monitoring.” – 7 similar comments

– “The on-line monitoring will be an engineering

change…make sure we can justify the cost with the

time savings...”

– “High Eff Removal of Key Detrimental Impurities

sounds great but too costly…”


– Only fund work to support cost savings – Online

Monitoring Technologies 2017

$0K leveraged funds

2018

$0K leverage funds

Median = 2.0



Online Iron AnalysisAn Assessment of Possible Technologies (TSG), In-Plant Demonstration (Base)


Measurement of feedwater iron is required for all BWRs and

PWRs (secondary)

Currently, plants manually collect corrosion product filters from

an integrated feedwater sampler, and then have those filters

analyzed

– Current analytical techniques are time consuming

Online measurement could significantly reduce resources

Two Phase Project

– Phase 1: Comprehensive technology assessment of online iron

analyses technologies (2016-2017 PWR TSG Project)

– Phase 2: Perform field trial to compare current technology with most

promising on-line monitoring technology (this project, 2018-2019)

S. Choi


Applicable for all power plants

(PWRs, BWRs, and Fossil

Units)

Online Iron AnalysisAn Assessment of Possible Technologies (TSG), In-Plant Demonstration (Base)

Online measurements

– Save personnel time and cost

– Provides for more actionable

measurements

A successful plant demonstration will

allow utilities to realize these benefits

and provide technical data to support

replacement of integrated sampling

with online measurements




Fundamentals

Chemistry Benchmarking and Trending and

Chemistry Modeling RFAs

2017-2018 Scope for

Chemistry Monitoring and Assessment (CMA), Chemistry Software, and MULTEQ



Chemistry Benchmarking and Trending

Collection and evaluation of fleet wide water chemistry data is an important step in ensuring the goals of optimized water chemistry control are met

Goal is a robust and global database – providing direct value to EPRI members and related EPRI projects

Project types

CMA Databases

Benchmarking

reports

North America(BWR, PWR, and CANDU*) Europe

(BWR, PWR* and VVER*)

Asia (BWR and PWR*)

Mexico (BWR)

Africa (PWR)

*Growth areas for the databases

South America (PWR*)


BWR CMA – Proposed 2017-2018 Scope

2017 – Multiple annual summary reports

(downloadable and plant-specific) BWR Sampling Summary

Deep Bed Resins And Precoat Materials

BWR Mitigation Summary

BWR Chemistry Summary

BWR Shutdown Chemistry and Dose Summary

– Explore and test alternate data transmission options NuclearIQ collaboration

– Work on building advanced relational database

2018– Explore and test online access options to BWR standardized

benchmarking graphs


PWR CMA – Proposed 2017-2018 Scope

2017– Online access to standardized benchmarking graphs

Focus on chemistry guidance control parameter

Includes selection and filter options

Plants of your utility will be identified

– Explore and test alternate data transmission options

NuclearIQ collaboration

Direct upload via webpage interface

2018– Expand online data access options based on user feedback


Improving CMA Data Transfer

It is recognized that data transfer is a burden on utilities

EPRI has worked over the years to ease this burden– Data Transfer Tool – Information Technology security changes make this difficult to

manage

The New Opportunity

GCR’s NuclearIQ Product is now

managing most data in the US and

Canada

– Partnering with GCR could greatly reduce

the burden on utilities to send data

The process could be replicated with

other “large scale” data management

packages being used by other utilities

Status and Process GCR has provided a list of all

parameters being handled by NIQ currently

EPRI is matching those parameters to the CMA names

Envisioned Process – NIQ automatically generates a file (likely

.xml type) containing all the CMA data from a plant

– The utility transmits the file to EPRI periodically



Chemistry Modeling

Software tools enable the practical application of chemistry models

– ChemWorksTM Tools, CIRCE, the Plant Chemistry Simulator, and the MULTEQ Database

Near Term efforts related to major revision of ChemWorks™, continued review of MULTEQ database species, and improved application and use of available tools

Longer Term efforts focus on development of a new ion exchange module, and broadening the application of the software to meet BWR, CANDU and VVER design needs

Project types

Development of

computational

tools

Assembling

thermodynamic

data


EPRI Chemistry Software Products

ChemWorksTM

Tools

MULTEQ Solubility Calculator

Hideout Return Calculator

Shutdown Calculator – BWR

Shutdown Calculator – PWR

PWR pH Calculator (.dll)

Plant Chemistry Simulator (PCS)

System Mass Balance

Purification

Hideout

Decomposition

CIRCE

PCS

Simplified CHECWorks (FAC)

Iron Transport

SG Deposition

SGBD Resin

SMART ChemWorksTM

(web-based)

PCS

Data Transfer Tool (DTT)

Finger Print Technology

MULTEQ Thermodynamic Database

Supplemental


Update Schedule

ChemWorksTM Tools

– Version 4.2 released 2015

– Version 5.0 scheduled for 2017

Plant Chemistry Simulator

– Version 4.2 scheduled for October 2016

CIRCE

– Version 2.0 scheduled for December 2016


ChemWorks Users Group Funds

The ChemWorks Users Group will become part of the Base Water Chemsitry Program in 2017– Funding (~190K) is secured for the program 2017-2019

Users Group Scope– Currently provides tech transfer assistance with

Chemistry Software (dedicated support and training opportunities)

This will likely continue although on an as-need basis

– Chance to utilize some funding for additional tech transfer

For example topical training (PWR secondary amine selection, guideline revisions, etc.)


MULTEQ DatabaseFundamental RFA – Chemistry Modeling: Collaborative with FRP, SGMP and NSERC*

Key R&D, software tool supporting technical

R&D, guidance bases, risk assessments and

plant operations

– Under development since the 1980s

– Periodically updated

– Database Committee: group of experts in

thermodynamics, solubility measurement, and

plant applications

Objective

– Provide key models of high temperature

speciation allowing for calculations of pH,

precipitate formation, and conductivity in light

water environments

2017-2018 Scope of Work

– Publish Rev. 9 of Database in 2017

KOH/borate species, zinc acetates and

silicates, HCl, Ar, Sb** species

New and update boric acid and ion pair

species

– Continue species review

Ammonium/ammonia and other amides,

Zinc/ammonium complexes, Ca/Na sulfates

– Species development

Advanced amines (DEHA, etc.)

– Incorporate recent work

High Temperature Boric Acid Speciation

Collaboration with Canadian Nuclear

Industry

*Natural Sciences and Engineering Research Council of Canada

**Materials Aging Institute (MAI) work being leveraged


Parallel Work to MULTEQ Database

Evaluation of High Temperature Speciation of Boric Acid (P-TAC and Chem Co-funded)

Significant extension of physical property data to high temperatures and addition of Li, Na, and K ion pairs

Report to be published in 2016

Impact on pH calculation being evaluated

Evaluation of Water Equilibrium Constant, Kw

(SGMP funded)

Determine if an update to Kw is necessary

Potential Impact of Change

– Major effect expected to be high temperature primary system calculations

– IAPWS pHT’s lower than MULTEQ at high temperatures and difference increases with temperature

Borate Ion-Pair Formation ConstantsLog10 K vs. Temperature (T / K)

25 °C

350 °C

175 °C

LiB(OH)4 this work

KB(OH)4 this work

NaB(OH)4 Pokrovski et al. (1995)

NaB(OH)4 this work

Li+ + B(OH)4- LiB(OH)4

0

MULTEQ Database Committee is involved in review of all work of this type

* Based on 2005 Bandura and Lvov correlation

11.1

11.3

11.5

11.7

11.9

12.1

12.3

200 210 220 230 240 250 260 270 280 290 300 310 320 330 340 350 360

pK

w

T °C

IAPWS 2007

M&F

pKw (Izatt)

11.1

11.3

11.5

11.7

11.9

12.1

12.3

200 210 220 230 240 250 260 270 280 290 300 310 320 330 340 350 360

pK

w

T °C

IAPWS 2007

M&F

pKw (Izatt)

200 225 250 275 300 325 350

T°C

12.3

11.9

11.5

11.1

pK

W


NEW EPRI Collaboration with Canadian Nuclear IndustryPeter Tremaine – NSERC Industry Research Chair (IRC)

NSERC/UNENE Senior IRC (Awarded January 1, 2016)– Mission “to provide the understanding and quantitative data needed to model the

chemistry of aqueous systems up to extremes of temperature and pressure”

– Funded by Canadian Industry (NSERC, UNENE, COG, NWMO, and University of Guelph) and EPRI: Total funding ~1.9M (5 yrs.)

Tech transfer centers around expanding

heavy water modeling capabilities and

making part of MULTEQ

– Note: a separate project would need to be

proposed to update the code for heavy water

modeling (~2019)

Four Research Projects

D2O isotope effects (CANDU Primary)

Metal Complexes & Hideout (CANDU & PWR Secondary)

Model Actinides & Fission Products (“Bonus” –Radiation Fields or Alpha Contamination)

Organic Solutes (CANDU & PWR Secondary)


Other Chemistry Projects Outside of Base

PWR and BWR Chemistry TSGs

Flexible Operations TAG


BWR and PWR Chemistry TSG Projects

PWR Chemistry TSG R&D Scope

Work Expected to Complete in 2016

– PWR Reactor Coolant Pump Shutdown Practices

– Filtration Evaluation

– Lithium Addition Evaluation

Completed: Optimized Lithium Addition on Plant Startup: PWR Chemistry Technical Strategy Group, June 2016, (3002008184)

New Projects for 2016

– PWR Primary Chemistry Modeling under MutlipleAlkali Chemistry (KOH for pHT control)

– Online Iron Analysis: An Assessment of Possible Technologies

– Hydrazine Alternatives: A Comprehensive Evaluation

Work to Complete in 2017

Evaluate Reduced Sampling Frequencies

Davis-Besse Gamma Scan Following Zinc Application

BWR Chemistry TSG R&D Scope

Work Completed in 2016

– BWR Condenser Inleakage Sourcebook

Completed: BWR Condenser Leak

Sourcebook: BWR Chemistry Technical

Strategy Group Report, January 2016

(3002007414)

– XRF Standards for Analysis of Metals

Completed: Presentation at Feb. 2016 BWR

Chemistry TSG meeting

Work to Complete in 2017

– Demo of Silica Quantification in BWR

Feedwater (Dresden and Clinton demos in

2016) – Technical Report in 2017

New Projects for 2017+

– Under review by TSG members


Chemistry Control during Flexible Power OperationsFlexible Power Operations Technical Advisory Group

Scope completing in 2016

– Evaluation of available PWR and BWR chemistry OE to understand impact of flexible power operation on chemistry control

– Evaluation of flexible power operation on PWR crud transport

Scope continuing into 2017+

– Chemistry support for plant evaluating and moving to flexible power operations

– Continued analysis of new data generated by plants operating flexibly

– Co-funding of online analysis of coolant anions demonstration (Chem. Project)

– Evaluation of flexible power operation on BWR crud transport

New Flexible Power Operations TAG cockpit for more information on full program scope


2017-2018 Water Chemistry PortfolioIncluding TSG and Non-Chemistry Program Funded Work


Sourcebooks)


(2015-2017)


(2016-2018)


(2018-2019)*



Chemistry Control for Flexible Power Operation

(2015-2018)

Chemical Mitigation



Hydrazine Alternatives: Demo (2018-2019)*


Li-7 Recovery Technology (2015-2017)

Hydrazine Alternatives: Current Tech Assessment

(2016-2017)








(2018-2019)*





(2015-2018)


NPP (2016-2017)



(2018-2019)*

Davis-Besse Gamma Scan Following Zinc (-2017)



(2016-2017)

On-Line Iron Analysis: Demo (2018)*

On-Line Iron Analysis: Tech Assessment (2016-2017)

Modeling of Multiple Alkali Chemistry (KOH)

(2016-2017)

Evaluation of Optimized Sample Frequency

(2015-2017)

Silica Quantification in BWRs: Demo (2015-2017)

Base Funded Work Base Fund with Modification New* TSG Funding Other Funding


2017-2018 Water Chemistry Recommended Portfolio Summary


Sourcebooks)


(2015-2017)


(2016-2018)


(2018-2019)*



Chemical Mitigation

Effect of Amine Decomposition Products on Crack Growth Rates

(2017-2019)*

Hydrazine Alternatives: Demo (2018-2019)*









(2018-2019)*





(2015-2018)


NPP (2016-2017)



(2018-2019)*



(2016-2017)

On-Line Iron Analysis: Demo (2018)*

Funded Work Fund with Modification New*


International Nuclear Plant Chemistry Conference 2016

The Brighton Dome, Brighton, UK

2-7th October 2016

Upcoming Industry Conference

Technical paper to cover the following topic areas:

PWR VVER & CANDU/PHWR Operating Experience Pressurized Water Scientific Studies BWR Operating Experience Boiling Water Scientific Studies Secondary Water Chemistry (Steam Cycle) Auxiliary Systems, Water and Waste Treatment System Life Time Management and Plant Aging Chemistry for Nuclear New Builds Water Chemistry in Alternative Reactor Designs Fukushima Response Radiation Chemistry and Electrolysis Workshop

Contact:

Keith Fruzzetti, [email protected]

http://www.npc2016.net/

Draft Program Posted

mailto:[email protected]

http://www.npc2016.net/


2018 International Water Chemistry Conference

• Organized by EPRI

• San Francisco, CA

• September 23 – 28, 2018

International Water Chemistry Conference

EPRI TO ORGANIZE THE 2018 NUCLEAR

POWER CHEMISTRY CONFERENCE IN

SAN FRANCISCO CALIFORNIA, USA


BACKUP SLIDES


Continuing Project Slides



Chemistry Guidance (Guidelines, Sourcebooks,

Technical Basis for Regulation)Continuing Projects


PWR Secondary Water Chemistry Guidelines Revision 8 (Continuing Project)


– The PWR Secondary Water Chemistry Guidelines is based on research and operating experience to

provide state-of-the-art water chemistry guidance – allowing PWR operators to optimize secondary

chemistry to reduce equipment corrosion and enhance component reliability (e.g., steam generators and

turbines)

R&D

• Materials testing

• Modeling and simulation

• Benchmarking and trending

Tools

• Sourcebooks

• Advanced treatment chemistries

• Chemistry databases

Guidance

• Chemistry control limits

• Corrective actions

• Chemistry monitoring and diagnostics

– The key technical issues being addressed are:

Interim Guidance (2) and Review Board Inquiries (5)

Steam Generator Layup (wet or dry)

Corrosion product transport monitoring

Steam chemistry guidance

Update on dispersant and film forming amines

Condenser in-leakage appendix (NEW)

Hydrazine / Oxygen control

Application of improvement factors (Alloy 800, denting work)

Guidance for Advanced Light Water Reactors

Silica

Objective: To develop Revision 8 of the Guidelines for the benefit of the industry


PWR Secondary Water Chemistry Guidelines Revision 8 (Continuing Project)

Planned Schedule

Meeting #1

– May 12 – 14, 2015 at the EPRI office in Charlotte, NC

Meeting #2

– October 27 – 28, 2015 at the UNESA office in Madrid, Spain

Webcasts: Discuss key items from first two meetings / path forward

– November 17 & 19, 2015

Meeting #3

– March 22 – 24, 2016 at the EPRI office in Charlotte, NC

Final Draft Revision 8

– Summer 2016

Final Review and Comment period by Rev 8 Committee

– Resolve comments and incorporate as appropriate

Industry Review and Comment

– Resolve comments and incorporate as appropriate

Revision 8 Committee Endorsement

Submit Revision 8 into the SGMP Endorsement Process

– Fall 2016

Publication of Revision 8

– Spring 2017

Minimizing Dose

Reducing Radiation

Fields

Accurate Reporting

Optimized Waste

Storage

EPRI

Chemistry Program

Minimizing material

degradation, improving

asset protection, and

reducing source term

Auxiliary

Chemistry


Revision to the Condensate Polishing Sourcebook

Project Description/Tasks

The existing version of the sourcebook was issued in 2004. A revision is

needed to update the document in the following areas:

• Expanded use of advanced amines in PWR plants and the increased

experience with amine-related fouling of condensate polisher resin.

• Transition at some plants from using full-flow condensate polisher

systems 100% of the time while at power, to use only during plant

start-up and as-needed.

• Several new media offerings including macroporous and orthoporous

ion exchange medias.

• New media retention element designs and fabrication practices.

• Significant advances in condenser integrity, and condensate polisher

operating practices in the industry.

Breadth of Applicability

• Applicable to all BWRs and PWRs (and fossil plants) worldwide.

PM: Joel McElrath


Revision to the Condensate Polishing Sourcebook

Benefits

• The Condensate Polisher Guidelines provide state-of-the-art

water chemistry guidance that allow BWR, CANDU, PWR,

and VVER operators to update their condensate polisher

chemistry programs to assure maximum chemical efficiency

and enhance component reliability.

• A committee of industry experts is used to develop these

revised Guidelines, incorporating the latest field and

laboratory data on condensate polisher performance issues.

• The expanded operating experience will provide utilities with

cost-effective strategies for condensate polisher

management and operation.

Schedule

• 2016 – 2017



Management of Corrosion product Behavior and Impacts

Continuing Projects


Metal Surface

or Oxide

Hydrophilic end

(Attaches to metal /

oxide surfaces)

Hydrophobic end

(Repels water)

PWR Secondary Side Filming Amine Application

2015 – Project initiation

Background/Need

Filming amines (FA) have been applied at fossil plants as a

means of protecting carbon and low alloy steel components,

especially during periods of long layup

EPRI has sponsored a number of programs related to use

of filming amines for fossil plants

Recently, a filming amine has been applied at Almaraz

Literature Review Update (Complete)

Specification Development (Complete)

Identification of Potential Chemicals (Complete)

Test Program Development/Planning (Complete)

Qualification Testing


PWR Secondary Side Filming Amine Application

2015 – Project initiation (continued)

Overall Project Objectives

To initiate an effort to qualify a FA and complete technical

tasks in preparation for conducting a plant trial to evaluate

the effects of the FA on PWR secondary system

performance

Value/Benefit

To qualify a FA for use in nuclear plant systems in order to

help to minimize the accumulation of corrosion products in

PWR steam generators


Applicable for global PWRs

Condenser Hotwell Inspection

Condenser Hotwell (close-up view)


Chemistry and Radiation Safety Research Focus Area:

Radioactivity Generation and Control (Source Term)

Continuing Projects



Chemistry Strategies for Surface Passivation Why –

– All reactors and all metal surfaces are affected

– Metallic surface exposed to high-temperature water will corrode

– Corrosion products exposed to neutrons will activate

– Activated corrosion products will generate radiation fields

What –

– Identify novel surface passivation approach that minimizes metal releases,

corrosion rates, and/or activity buildup – during component production

and/or in situ – before in service and after decontamination

– Initiate technology transfer of proof-of-principle candidates

So what –

Lower corrosion leads to

higher equipment reliability,

less maintenance,

lower radiation fields and reduced worker dose

Stopping Metal Release is Most Effective Course of Action

C. Gregorich


Project Approach - Progress

Phase 1 – Review State-of-the-Art Knowledge

Phase 2 – Test most promising technologies – in progress

Phase 3 – Develop scale-up protocols and validate

Phase 4 – Development of plant demonstration criteria

2015 2016 2017 2018

Phase 1

Phase 2 Phase 4

Phase 3


Chemistry Strategies for Surface Passivation

Collaboration with Materials Aging Institute



Hydrophobic Coatings - Reduce Contamination/Worker Dose

Key Research Question:

Can commercial hydrophobic coatings assist in

decontamination control and dose reduction? Does their degradation introduce detrimental species?

What is their durability?

How effective are they?

Can a standard qualification protocol

be developed?

What are reasonable criteria?

Project Approach:

1) Survey globally nuclear and non-nuclear industry – best practices

and utilized hydrophobic coatings. Review chemical and physical

surface modification treatments and technologies fora. Durability of hydrophobicity,

b. Release of potential detrimental species,

c. Compatibility with materials of construction.

2) Create a state-of-the-art knowledge base

3) Identify gaps and opportunities.

4) Conduct demonstration under plant-like conditions.

5) Develop criteria for plant demonstration, verification and

validation.

Objective:

Assess hydrophobic coatings effectiveness

and durability

Evaluate formation/release of species

detrimental to asset protection and fuel

reliability

Develop criteria of performance

acceptance

Value:

Assist plants in coatings selection

Improve contamination control –

fewer PCEs and lower dose

Saves cost – reduces

qualification testing

decontamination and

contamination control efforts

Particulate Surface Contamination Causes Radiation Fields & PCE’s, i.e. Worker Dose

2016

2017


Hydrophobic Coatings - Progress

Review of current use in nuclear and other industries in progress

Survey questionnaire has been send to members

– Responses to-date:

24 responses – 13 utilities (2 non-US) – 18 sites

3 utilities – 6 sites – are using/testing hydrophobic coatings

Applications – coating of stainless steel surfaces

– Sample sinks

– Spent fuel pool tools

– Casks (removal of fuel from spent fuel pool to dry cask storage)

– Steam Generator downdraft table and water filter

2 types (Rustoleum Never Wet & Ultra Ever Dry) – applied per manufacturer instructions as

aerosol

Limited independent/verifying performance testing


Hydrophobic Coatings – Next Steps

Finalize

– Review of use in other industries

– Survey of membership – if you’d like to add, send request to

[email protected]

Select most promising coatings for testing in addition to

coating currently used by members

Perform durability and performance testing

– Under common conditions (chemistry and radiation)

– Assessing

Initial releases of potential detrimental species

Releases of potential detrimental species over simulated lifetime

Lifetime of hydrophobic effectiveness

WebCastWhite Paper4th Qtr 2016

Final Report2017

mailto:[email protected]



Impact of Micro-Environment on Radiation FieldsN

eed

Radiation fields are: controlled by local (system) specific

physicochemical conditions impacted by intended and unintended

operational changes

Ob

jecti

ve

Assess impact of chemistry program changes on local radiation fields

Identify local radiation field response variations to the same change

• Survey and evaluate literature on colloid formation under LWR conditions.

• Survey global industry data to identify situations and collate experiences

Phase 1in progressTR in 2016

Experimental program to investigate under specified local conditions:

• Effect of radiation on corrosion product deposition

• Colloid formation, transport, and deposition behavior

Phase 2in planning2016-2017

Expands fundamental knowledge of radiation field

generation in multivariate primary coolant systems

responding to implemented chemistry mitigation

strategies for asset protection, radiation field

and source term reduction

C. Gregorich




Silver and Antimony Impact on Radiation Field Control

2.5 g cobalt or 1g silver activate to 60Co or 110mAg, resp.,

and cause radiation fields of equal magnitude.

Silver and antimony* sources might be more abound than previously thought: reactor vessel head seals,

reactor control rod cluster assemblies, metal O-rings, valve seat seals, lead-free solder, brazing and

welding material – and environmental sources

Silver and antimony chemistries are complex – in particular, under

changing redox, pH, and temperature in a radiation field – and

therefore, identification and quantification can be challenging.

Ob

jec

tive

Identify sources

Develop better knowledge of high-temperature Ag and Sb speciation,solubility and reaction dynamics

Control impact on radiation fields

a) though tools, technologies, strategies or alternate component materials

b) by eliminating ingress of silver and antimonyc) removal the elements effectively before their

activation, or their activation products

Sc

op

e/A

pp

roa

ch

Phase 1 – 2016

Survey & review global industry knowledge base

Develop experimental scope of work

Phase 2 – 2017-2018

Detailed plant monitoring program

Lab testing – speciation, solubility, and reaction dynamic under simulated conditions

Va

lue

/Be

ne

fit

The knowledge gained and opportunities identified will guide the global fleet in achieving excellence in radiation field control. Furthermore, the results will assist new builds by learning from the current fleet’s experiences and knowledge.

*Fine print: Equivalent masses of nickel or antimony activate to 58Co or 124Sb, resp., and cause radiation fields of equal magnitude.

C. Gregorich





Continuing Projects


Demonstration of Enhanced Online Monitoring of Ionic Species in

BWRs and PWRs (New Project)

Background/Need

Chemistry Guidelines now require more frequent analysis of

ionic species such as chloride and sulfate

Current grab sampling process increases technician radiation dose

and the potential for sample contamination

Current analytical techniques are time consuming…many require

hours for results

Accuracy and precision of current techniques is limited for some

water streams (sub-ppb concentrations difficult to attain)

Project Objectives

•Provide more immediate indication of out-of-specification conditions

or adverse trends, allowing for more timely corrective actions

•Improve the accuracy and precision of results

•Maintain ALARA goals and optimize chemistry technician workloads

Lab on a Chip

PM: Susan Garcia

http://en.wikipedia.org/wiki/File:Glass-microreactor-chip-micronit.jpg

http://en.wikipedia.org/wiki/File:Glass-microreactor-chip-micronit.jpg


Demonstration of Enhanced Online Monitoring of Ionic Species in

BWRs and PWRs (New Project)

Workscope

1. Select analytical technique from current 2015 base-funded Chemistry Project

2. Identify host plant site(s) for demonstrations

3. Develop test matrix

4. Coordinate and support plant demonstration(s)

5. Compile Technical Report of results

Benefits

•Allows for rapid identification of adverse trends and rapid response for water

treatment or system isolation

•Potentially improve precision of analytical results using an on-line method that

eliminates sample handling, sample contamination and reduces technician exposure

Schedule

•2016 -2017 Project

http://www.google.com/url?sa=i&rct=j&q=&esrc=s&frm=1&source=images&cd=&cad=rja&uact=8&ved=0CAcQjRxqFQoTCM-N6-P-g8cCFcSYlAodgy8A8Q&url=http://www.bioprocessonline.com/doc/agilent-showcases-first-lab-on-a-chip-product-0002&ei=0LC6Vc_lI8Sx0gSD34CIDw&bvm=bv.99261572,d.dGo&psig=AFQjCNED3RIJDwT_WLVy8gEiaU2cE2eNNA&ust=1438384603427005

http://www.google.com/url?sa=i&rct=j&q=&esrc=s&frm=1&source=images&cd=&cad=rja&uact=8&ved=0CAcQjRxqFQoTCM-N6-P-g8cCFcSYlAodgy8A8Q&url=http://www.bioprocessonline.com/doc/agilent-showcases-first-lab-on-a-chip-product-0002&ei=0LC6Vc_lI8Sx0gSD34CIDw&bvm=bv.99261572,d.dGo&psig=AFQjCNED3RIJDwT_WLVy8gEiaU2cE2eNNA&ust=1438384603427005


2017-2018 Work Plan

Unfunded Proposals


End of Plant Life Chemistry Control OptimizationConsideration of Cost Minimization and Recovery


Recently announced plant shutdowns were relatively unexpected

Guidance for preparing for such shutdowns is limited

Chemistry control programs could be modified to maximize resources and potentially provide economic benefit to the operating utility

– Mitigation technologies…stop, reduce, continue?

Hydrogen and noble metal injection in BWRs

Zinc addition in PWRs

– Dose reduction technologies…continue?

Depleted zinc addition in BWRs and PWRs

Source term reduction (CRB, valve replacements)

– Steam generators

Use of dispersants

– Monitoring and analysis requirements…can we scale back?

Equipment considerations

– Sell or move equipment to other sites

– “Run to empty” for some systems

– Leftover consumables (zinc, resin, septa, chemicals, etc.)

system shutting down…

S. Garcia


U.S. BWRs in the short term

Also plants in Spain, Sweden,

Switzerland, Taiwan

Some plants in Japan will not

be restarting

Economic conditions are

unknown at this time, so

preparation is key to good

decision making

End of Plant Life Chemistry Control OptimizationConsideration of Cost Minimization and Recovery

Careful, detailed evaluation of chemistry

control programs, systems, monitoring and

consumables prior to shutdown can benefit the

utility in a number of ways:

– Economic recovery

– Dose control

– Orderly shutdown



Proposed for co-funding with Chemistry and Decommissioning


Interaction of Boric Acid and SilicatesGap Assessment

Silica limits in PWRs and BWRs are largely based on

concerns associated with precipitation of silicate species

in fuel crud and work completed in 1992*

– BWR fuel crud scrapes clearly contain silicates including

Zn-silicates, but PWR fuel crud observations of silica are

limited

Utilities are driven to implement sometimes expensive

technology to reduce silica concentrations (spent fuel

racks are the major source)

– Recycling of boric acid increases the problem

Recent evaluations completed in the MULTEQ Database

committee suggest boric acid may increase silicate

solubility reducing the risk of precipitation

D. Wells

*TR-107992

MULTEQ

without B-Si ion pair

MULTEQ

with B-Si ion pair


Interaction of Boric Acid and SilicatesGap Assessment

Objective

– Evaluate the currently available data related to silica solubility, plant and experimental observations, and benefits of technically based silica limits

– This project will require engagement with fuel suppliers as limits are largely fuel supplier applied

Scope

– Review available thermodynamic data

– Review fuel crud data for silica observations

– Review of chemistry observations

– Evaluate benefits to the plants of technically based silica limits

– Develop potential follow on projects

Value

– Control of silica can be an expensive task and guidance is largely based on operating experience rather than technical basis

– This project will establish the potential utility benefits of work to provide technical based silica limits

Lower cost of utilities to meet current requirements

Lower barriers to implementation of other cost and dose saving measures (zinc)

Reduce sampling and analysis requirements

Global applicability

– All light water PWRs operate with boric acid and manage silica contamination


Proposals also made to FRP for funding


Effects of Radiation on PWR Primary System Chemistry Reaction

Kinetics during Shutdown – Assessment and Plan Forward

Objective: To provide a more detailed understanding of the overall reaction kinetics of deposit materials during

the shutdown evolution in order to optimize shutdown chemistry.


– The kinetics of corrosion product deposit reactions during PWR shutdowns are not well understood. During shutdown of PWRs, several chemistry and temperature manipulations occur, including:

Reduction in temperature, increase in boric acid (and resulting decrease in pH), reduction in dissolved hydrogen, addition of hydrogen peroxide (resulting in oxidizing conditions)

– The impact of chemistry parameters on crud dissolution kinetics hasbeen studied, but the impact of the radiation field on the reaction kinetics – anticipated to be significant – has not been well evaluated.

– Previous work, not yet published (but major findings were incorporated into the Primary Water Chemistry Guidelines) will be leveraged and included.

– A better understanding of the reaction kinetics during shutdown evolutions could lead to better support of the following:

Shorter outage times

Lower personnel radiation exposures

Lower risks of deposit related fuel performance issues

40°C60°C80°C100°C120°C

104°F140°F176°F212°F248°F

0.0001

0.001

0.01

0.1

1

0.0025 0.0026 0.0027 0.0028 0.0029 0.003 0.0031 0.0032 0.0033

Inverse Absolute Temperature (1/K)

Re

ac

tio

n R

ate

Co

ns

tan

t (g

/s-m

2)

Eact = 55.8 kJ/mol

k0 = 2.5 x 106 g/s-m

2

Minimum values (saturated effluent)

Ni dissolution rates

no radiation field

K. Fruzzetti


Effects of Radiation on PWR Primary System Chemistry Reaction Kinetics

during Shutdown – Assessment and Plan Forward

Project Approach

Task 1: Update the literature review and experimental testing that was done in previous years.

Task 2: Develop a test protocol to evaluate the effects of radiation on reaction kinetics during shutdown. (This project

includes only the development of the testing protocol, not the actual execution of the testing.) This includes:

– Estimation of the effect of radiation on the reactions of interest based on theoretical consideration. Includes consideration of the various

types of radiation present in the core during shutdown (residual alpha, neutrons of various energies, gamma, etc.).

– Identification of reactions to be evaluated, including the range of important species (e.g., the continuum of non‐stoichiometric ferrites with

nickel ferrite and magnetite as end members) and the extent of reaction that is important and should be evident in the testing.

– Identification of needed analytical techniques. Many of the reactions under consideration are difficult to measure. This task will identify the

analytical techniques required to monitor the reactions of interest over the extent of reaction necessary.

– Identification of testing parameters. The data necessary to support optimization of chemistry maneuvers must be generated. This requires

collection of data over a range of options for different parameters such as temperature, pH, and peroxide concentration. This task will identify the

test conditions that will provide the most valuable data for the least cost.

– Identification of a test facility. The anticipated testing will require a radiation source. Several sources are available for such testing, including

private facilities (e.g., SouthWest Research Institute), universities (e.g., University of Maryland, College Park), and government laboratories (e.g.,

Idaho National Laboratories).

– Preliminary cost estimates. Based on the results of the above tasks, a preliminary cost estimate for the anticipated testing will be developed.

This will include requesting quotes from potential exposure facilities.

Proposed Duration and Timing: 2018 (10 mo.)


Dispersant Use Beyond PWR Secondary SystemsFeasibility Evaluation


Corrosion products cause significant problems for many plant systems/components:

– Under deposit corrosion

– Heat transfer loss

– Elevated radiation fields

In severe cases, corrosion product deposits can create conditions that challenge fuel cladding integrity.

Dispersant has been demonstrated to provide significant benefits:

– Reducing the rate of iron accumulation in steam generators (SGs)

– Recovering SG heat transfer efficiency

– Reducing fouling of plant systems (e.g., removal of existing “dispersible” corrosion products)

Objective: Evaluate the feasibility of dispersant application for mitigating deposit formation, fouling and radiation fields in key systems / locations (outside of the PWR secondary system), and develop a plan to go after the most promising application(s).

K. Fruzzetti


Dispersant Use Beyond PWR Secondary Systems – Feasibility Evaluation

Project Approach

Identify key systems / locations in BWRs and PWRs. Possibilities include:

– Residual Heat Removal (RHR) System. Flushing of the RHR system for removal of corrosion products may be significantly

improved by application of dispersant (so as to not introduce them into the primary system when placed in operation).

– Heat Exchangers. Iron oxides deposit on heat exchanger tubes, increasing resistance to heat transfer and thus reducing thermal

performance. Targeted dispersant application for removal of these deposits may significantly restore thermal performance. In

primary systems these deposits are often activated and thus removal may reduce out-of-core radiation fields.

– Stator Cooling System. Loss of cooling capacity due to plugging of hollow strands of stator bars or clogging of strainers, or

crud/oxide deposition on rectifier tubes, has been observed at many power stations. Excessive stator temperature and loss of flow

has resulted in power reductions and unplanned plant shutdowns. Dispersant application could significantly mitigate these issues.

– New Surface Conditioning. Prior research by EPRI indicates that PAA can remove the non-protective portions of the oxide layer

without affecting the protective layer. This feature of PAA could be used to remove corrosion products from new or recently

decontaminated components, preventing them from being deposited in other locations in the system.

Quantify the potential benefits

Evaluate how best to apply the technology, including potential limitations and derivative impacts

Identify two or three most promising applications

Develop a plan to address gaps, with a plan for the path forwardProposed Duration and Timing: 2018-2019 (20 mo.)


High-Concentration Dispersant (PAA) Corrosion Testing Carbon Steel at Elevated Temperature


Carbon steel exhibits increased corrosion rates when exposed to PAA

– Small with limited or negligible consequences at low PAA concentrations (e.g., 100 ppb or less as expected in typical online applications)

Increase of only about 0.00001 in/yr (0.01 mpy or 0.00025 mm/yr) at 100 ppb PAA

– However, STP experience in 2016 (see CHEM 2016-01) demonstrated that a bounding maximum corrosion rate of carbon steel with 10% PAA and near feedwater temperature canbe about 0.05 in/yr (50 mpy or 1.3 mm/yr).

The concern with high PAA concentrations is in the injection line or in the carbon steel feedwater line just downstream of the injection location (if an injection stub/quill is not used)

– Injection line could use stainless steel (solution)

– Injection location could use a stainless steel stub/quill (solution)

– Injecting high concentration PAA at a very low flow rate and without an injection stub/quill is of significant concern as it could lead to a localized concentration of PAA (equivalent to the concentration in the injection line) at the carbon steel feedwaterpipe just downstream of the injection location.

Objective: Quantify the effects of PAA at high concentrations (up to 10 wt%) and PWR feedwater conditions (about 220°C) on the corrosion rate of susceptible carbon steel.

STP leak location (injection line)

K. Fruzzetti


High-Concentration Dispersant (PAA) Corrosion Testing of Carbon Steel at

Elevated Temperature

Project Approach

Testing in a refreshed (flowing) high-pressure

autoclave at appropriate feedwater conditions

meant to simulate the quasi-static conditions

expected in the plant:

– Two PAA concentrations (10% PAA and a lower

concentration) at a single elevated temperature (e.g., 220°C)

– A baseline test at room temperature to serve as a control

– Multiple carbon steel specimens at each test condition for

redundancy (and limited statistical evaluation)

– Quantification of corrosion rates through pre- and post-

exposure weighing (with post-test descaling)

– An evaluation of the effects of pre-filming on the corrosion

rate (e.g., through testing of at least one additional specimen)

– An evaluation of potential galvanic effects (e.g., through

testing of at least one additional specimen)

Results are expected to help address the

following:

– Determine whether existing carbon steel injection line

components are compatible with PAA addition (and, if so, for

what period of time)

– Evaluate the suitability of proposed injection configurations

that include carbon steel piping, fittings, and/or valves

– Determine appropriate NDE inspection frequencies,

component replacement schedules, and/or the necessary

degree of PAA dilution in the injection line (in the event that

an existing or planned configuration is judged unacceptable

for indefinite long-term use)

– Evaluate the potential for corrosion of FW piping locations

very close to the junction with the injection line where PAA is

not well mixed (applicable to all injecting units with

susceptible geometries, such as flush-mounted injection-line

fittings)


Will evaluate co-funding with SGMP and Engineering Programs (BOPC)



Effect of Ultra-Low Iron – HWC/OLNC – on Activity Transport

How do current BWR chemistry regimes affect activated corrosion product transport?

FFW Fe in 2000

2002

20042006

FW Fe Median is 0.15 ppb in 2015 vs. ~1 ppb in 2004

BWR FW iron concentrations have been reduced to Lower crud burden on core

Improve effectiveness of zinc injection

for radiation field reduction

BWR coolant regime transitioned to Low-hydrogen injection with

More frequent, lower concentration platinum injections

Current Observations:

Elevated Co-60 RW activities

Elevated, prolonged particulate releases

Cr-51 increasingly observed as activity and dose rate contributor

(shutdown releases, surface activities, particulates)

S. Garcia



Effect of Ultra-Low Iron – HWC/OLNC – on Activity Transport

Develop understanding of ex-core deposit formation processes under current water chemistry control practices with ultra-low FW Fe concentrations

Enhance the knowledge of incorporation and release processes of activated corrosion products into/from ex-core surfaces, i.e. radiation field generation and shutdown/transient particulate releases

Objective1) Review current chemistry practices and data –

(BWR CMA & SRMC) and determine gaps

a) Identify bounding criteria of chemistry conditions and plants matching those

b) Solicit cooperation of selected plants for additional data gathering

4) Perform at least two subsequent outages gamma scans at selected plants at all recommended standard radiation field monitoring program points and selected additional locations (if feasible solicit host plant to perform remote isotopic monitoring during at-power operations for a whole cycle)

5) Formulate hypotheses of ex-core deposit formation under current BWR coolant conditions and develop white paper detailing a test plan to verify the hypotheses

ApproachResearch results will provide the basis and understanding to

Balance ultra-low feedwater iron conditions needed to ensure fuel reliability with minimizing radiation field generation in ex-core regions.

Inform future BWR water chemistry guidance

Guide the development radiation field reduction technologies and/or strategies

Value/Benefit



High Efficiency Removal of Key Detrimental Impurities: Development and Application of High Performing Media

Background

Utilities are severely impacted by certain chemical contaminants that exist at very low concentrations, but nevertheless

cause major issues on an industry wide basis:

– Pb (lead) is the most potentially significant contributor to stress corrosion cracking (SCC) of steam generator tubes – especially for the

replacement 690 fleet.

– Ni (nickel) is a major corrosion release contaminant into the primary system that when activated leads to the formation of Co-58 – which

is a major dose contributor in both PWRs and BWRs.

– Sb (antimony) has been identified as the major dose contributor in the low temperature portion of the primary system at many plants –

where most outage work is performed, leading to significant dose to workers.

– Ni-63 and Fe-55 are of particular concern in liquid effluents, with Fe-55 being one of the biggest dose contributors.

Innovative technologies have been identified to unleash a significant improvement in removal efficiency

– Metal Organic Frameworks (MOFs)

– Sequestration ligands (example of recent success: cobalt)

Objective: Develop a high performing media to significantly improve the removal efficiency (in kinetics and capacity)

of key detrimental impurities using existing polishing vessels (filter demineralizers or deep bed), leading to reduced

materials degradation, reduced plant radiation fields, and improved liquid effluents.

K. Fruzzetti


High Efficiency Removal of Key Detrimental Impurities: Development and Application of High Performing Media

1. Challenged by competing

ions

2. Needs mass action to drive

ion to resin, depleted with

ionic capture

3. Capacity limited to meet

requirement for integrated

charge balance

4. Limited to Coulombic

binding energy

Resin pore

Ion Exchange

INNOVATION

Metal Organic Framework (MOF)

30Å

NU-1000

• Strong Zr(IV)-O

• Water stable over wide pH range

• Mechanically stable

• Thermally stable > 500oC

• Tunable chemical and

physical properties

• Permanent porosity

• Ability to incorporate sequestration

ligand directly into the framework

1. Tailored for target species

2. Removes target species from

the water phase making it part

of the solid phase – renewing

mass action

3. Removes the need for charge

mediation

4. Binding energy can be

100,000x higher than

Coulombic energy

Sequestration Ligand (Example: Co)

+



X-ray Fluorescence Analysis for Light Water Reactors


Industry need identified at previous TAC meetings

– Issues with standards and non-representative results

Limited research project initiated within the BWR Chemistry Technical Strategy Group (TSG) in 2015 and work documented in conjunction with PWR dispersant application

– Limited funding to publish technical report from BWR TGS work and PWR dispersant work “buried” in appendix

– Need to provide a cohesive analysis of technology and issues

2018 Project will delve deeper into XRF analysis, use of standards and improvements for the industry

– Guidance on instrumentation methods and calibration standards

– Loading capacity evaluations and interference considerations

– Case studies at BWR and PWR sites

– Possible equipment to be evaluated

Oxford ED-2000 and X-Supreme 8000

Published Technical Report for industry use

S. Garcia


XRF used across the world-wide fleet

Reporting of accurate levels of metals in

plant water is important to fuel vendors

Results of case studies will be applicable

to plants around the world

X-ray Fluorescence Analysis for Light Water Reactors

Guidance on modifying instrumentation

methods or calibration standards

Better understanding of loading capacities of

ion exchange membranes

Minimization of laboratory errors

Confidence in reported values of metals for

fuel performance and radiation field control




BWR Plant Experience using CoSeq®


EPRI CoSeq® Powder available commercially from Purolite in late 2015

– Continue use evaluations documented in 2014* during development and plant demonstrations

Use provides a unique opportunity to evaluate impact on cobalt transport and ex-core film incorporation dynamics

– Need to understand CoSeq® use’s ability to perturb RCS cobalt levels and the time scales for changes

– Assess whether time correlations to fluctuations in ex-core dose rates or parent activation and release rates exist when driven by CoSeq®-produced perturbations in RCS cobalt levels

– Benefits of long-term use should be documented from first application

Scope

Monitor and document BWR RWCU Performance for Co-60 Removal

– Initiate collection of data necessary to evaluate impact of CoSeq®

– Where possible, assess changes in at-power, continuous cobalt control in the RCS

– Where possible, assess changes in S/D critical path to flood-up and RWCU maintenance Co-60 limits

– Measure against historical cobalt control prior to CoSeq® use

*3002003123

D. Wells


Co-60 is principle source of

worker dose in BWRs globally

CoSeq® resins are available

to plants worldwide through Purolite.

BWR Plant Experience using CoSeq®

Evaluate methodology for evaluating

quantification of RCS radiocobalt behavior

Field test of the degree to which CoSeq® use

might reduce dose rates experienced by plant

and outage workers – improved understanding

of benefits

Field test of the degree to which CoSeq® use

might alter shutdown critical path and hence

reduce outage power replacement costs.




Improved Quantification of Cobalt Source Term


Improve accuracy of measuring elemental cobalt in plant process streams

– Condensate, feedwater, heater drains, reactor water, etc.

Provide ability to perform overall mass balances

Identify region of origin or components contributing to elemental cobalt ingress

Detailed review of analytical instrumentation types

– ICP (all types), AA, XRF

Identify improvements in sampling and analytical techniques

Investigate colloidal cobalt recovery

– Review available filter types, particle retention

Provide industry detailed Technical Report of all findings

S. Garcia


Cobalt source term is an issue across the

industry.

Reduction efforts have varied by plant

type (BWR or PWR) and history of

operation.

“Driving dose to zero” should be a goal

for all plants.

Improved Quantification of Cobalt Source Term

Careful, detailed evaluation of the

elemental cobalt source term will allow

stations to better quantify cobalt

sources and effectively allocate

resources for reduction efforts.

Dose and exposure reductions due to

Co-60 should follow.



chemistry and radiation safety - amazon s3 · chemistry and radiation safety . technical advisory...

Documents