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IPS 2017 Conference

February 2017

Evolution of Power Plant Analytics

For improved corrosion control

1 Mettler-Toledo Overview

2 Why control power plant chemistry?

3 Key online measurements and how they are evolving

4 Brief Updates – Degas Conductivity, Organics/TOC, Intelligent Sensors

5 The Next Step – Online Chloride & Sulfate Measurement


METTLER TOLEDO is a leading global manufacturer of

precision instruments and services for use in
laboratories, manufacturing and process control.

 12,500 employees
 $2.4 billion USD turnover
 Worldwide presence with sales organizations in 36 countries

Our Solutions across the Value Chain

Laboratory Process Industrial Product Logistics Retail

Solutions Analytics Weighing Inspection Solutions Weighing

We offer solutions along our customers` value chain to help them:

 Streamline processes
 Enhance productivity
 Reach compliance with regulatory requirements
 Optimize cost and waste
Process Core Segments & Applications
Chemical and Pharma and Food and Power Micro-
Petrochemical Biotech Beverage Generation electronics

 Measure pH and  Measure pH, O2  Monitor O2 in  pH/ORP, TOC and  Control UPW in
conductivity in and CO2 in critical beverage conductivity in semiconductor,
chemical synthesis fermentation production steps make-up water photovoltaic and
treatment flat panel
 Measure turbidity in  Control pH and  Control and
phase separation conductivity in monitoring of CO2  Cycle chemistry
and filtration ultra-filtration and in sparkling monitoring with pH,  Measure TOC,
chromatography beverages O2, and Sodium / resistivity, pH/
 In-situ gas O2
Silica ORP in etching,
analysis in  pH/ORP control in  Turbidity control in
stripping and
blanketing and API synthesis separation  Measure pH and
inerting processes conductivity in
 TOC and Ozone
cooling water  Control
 Make-up water measurement in  pH and Cond
preparation recycle/reclaim/
treatment pure and ultra-pure control in sugar and
reuse waters
waters starch production  Waste water

Global Process Analytics Presence
R&D Centre and Production


R&D Centre and Production


Representative Main Office

São Paolo: Representative Branch Office MO Main Office
Production Manufacturing MO Branch Office
Why Control Power Plant Chemistry?

 Minimize corrosion
- Prevent leaks, contamination, catastrophic
- Prevent deposit of corrosion products

 Minimize deposits
- From minerals
- From corrosion products
- To maintain thermal efficiency
- To prevent under-deposit corrosion
- To avoid shutdowns and costs for cleaning

 Protect the Turbine!

Poor Chemistry Control Failures
Boiler Failures Turbine Failures
 Under Deposit Corrosion  Deposits
- Corrosion fatigue - Silica & Phosphate
- Hydrogen damage  Pitting
- Acid phosphate corrosion  Crevice
- Caustic gauging corrosion
 Flow-accelerate corrosion  Corrosion
- Single and Two Phase fatigue of blades
- most damaging and  Stress corrosion cracking of
blades or attachment points
 Stress-corrosion cracking

Key On-line Measurements - Tools

pH: Raise pH with ammonia, amines and/or phosphates to ~9

pH to minimize corrosion; protect RO membranes from scaling
Conductivity: Minimize dissolved minerals, assure water
purity, manage effectiveness of RO membranes

ORP: Control reducing agent (oxygen scavenger) such as


Dissolved Oxygen: Control to ppb levels to reduce corrosion

Chloride/Sulfate: NEW Protect the turbine, reduce risk of

corrosion & deposition and trace contamination detection
Sodium: Detect trace contamination levels in steam and
condensate to reduce corrosion.

Silica: Detect trace carryover in steam to prevent deposits on

turbine blades
TOC: Detect organic contamination in make-up water
treatment & in steam condensate

Process measurements for the entire cycle
MT & Thornton History/Brand
 Reputation on core technologies
 Quality, Service, Innovation
 Commitment to Power

Conductivity - UniCond w/ISM

 Better Accuracy with Digital
 Expanded Measurement Range
 Heart of the new DCC1000
pH measurements with pHure
 Best sensor for difficult application
 Better design and lower maintenance than

DO for Power
 High Performance and Optical
 Easier and lower maintenance than competition

Organics - TOC
 Cogen applications
 Steam Condensate testing
 Increasing interest in feed water testing
 Portable testing alternative to lab testing
IAPWS Minimum Instrumentation 10

 Cycle chemistry monitoring >>

- A range of additional
instrumentation (degassed
cation conductivity, silica,
TOC) may be required on
plants which have non-
generic problems.
 Makeup water treatment -
- Conductivity
- Cation conductivity
- Silica

For internal use - Confidential

IAPWS Cycle Chemistry Guidelines 11

 Treatment types
- All Volatile Treatment (Oxidizing)
(residual oxygen present)
- Oxygenated Treatment (oxygen added)
- Applicable to fossil plants with drum
units, with pressures ~17 MPa (~2500
psi), all-ferrous feedwater systems,
non-copper tubed condensers, with a
condensate polisher, and not cooled by
seawater or brackish water.

For internal use - Confidential

Degas Conductivity Overview
 Three conductivity measurements are available: specific,
cation and degassed cation
 Calculated pH, ammonia and CO2 measurements are
 Displays all measurements on a single M800 screen
 Trend graphs can be assigned for each measurement to
evaluate process over time; this is essential in plant startup
 High performance cation resin meeting nuclear plant
specifications; color change (green to purple) indicates resin
is exhausted and needs replacement
 A fully self-contained system
- Flow control built into the system
- Circuit breakers an included for individual components and easy
- Customer does not need to provide a cooling water connection
- No tubing or wiring runs behind panel; can be mounted on rack
or wall with easy access for maintenance

Organic Standards – TOC Measurement
ASME Recommendations - Drum Boilers
Drum Operation Psig 0-300 Psig 301-450 Psig 451-600

Pressure MPa 0-2.07 2.08-3.10 3.11-4.14

TOC Limits Less than 1 ppm Less than 1 ppm Less than 0.5 ppm
( & Oily Matter)

Drum Operation Psig 600-900 Psig 901-1500 Psig 1501-2000

Pressure MPa 4.15-6.21 6.22-10.34 10.35-13.79

TOC Limits Less than 0.5 ppm Less than 0.2 ppm Less than 0.2 ppm
( & Oily Matter)

EPRI Recommendations - Utility Boilers

Boiler Treatment Equilibrium Phosphate Phosphate
Method AVT or Oxygenated
TOC Upper Limit 100ppb 100ppb

Eskom Chemistry Guidelines – Demin Water for Coal Fired Plants

Upper Limit – 250 ppb Target Operating Range – 100 ppb

How is Organics / TOC measured?

Can be measured both on and off-line

▪ On-line for continuous measurement in the water sample panel for
incoming water quality or steam condensate return.
 Can divert problem water quickly before more damage can occur
▪ Off line for lab testing from multiple sample points or for quick
"trouble shooting" to identify source of organic contamination

ISM – Intelligent Sensor Management Concept

ISM® is METTLER TOLEDO's innovative platform for

digital process analytical measurement solutions.
With ISM …
 maintenance becomes predictable
 sensor handling is simple and
 lifecycle cost of instruments is reduced.
Application specific intelligence built into the sensor
electronics offers tailored solutions for the Power

Intelligent Sensor Management
Process measurements for the entire cycle
Comprehensive offering of advanced process analytics for complete pure
water cycle chemistry monitoring required for power generation applications

Powerful analyzers Multi-parameter transmitters Intelligent Digital Sensors

 Chloride/Sulfate for  Multi-parameter transmitters  UniCond® digital conductivity
maintaining contaminants for simplified operation and sensors for enhanced accuracy
below limits for efficient and in- reduced panel footprint and measurement range
spec operation  Touch screen and color for  Optical Oxygen sensors with
 Sodium for cation exchange & better interface reduced maintenance for
regeneration, turbine  Digital Techology stable ppb measurements
protection, and leak detection  ISM pH sensors for ease-of
 Calculated Values available
 Silica for anion exchange & use and accurate operation
regeneration and turbine  Available with Intelligent
Sensor Management (ISM) for  Available with plug-n-measure
protection functionality
enhanced accuracy and ease-
 TOC for corrosion control, of-use
reduced steam contamination
risks and leak detection 16
February 2017

Chloride/Sulfate Analyzer
High Sensitivity, Fully Automated
The need for chloride & sulfate measurements

 Reduce corrosion – transport – deposition

- Reduce risk of catastrophic failure
8 Chloride leads to pitting
8 Pitting leads to Chloride stress corrosion
- Minimize corrosion product deposition
8 Maintain efficiency
8 Prevent under-deposit corrosion
 Mitigate effects of cycling or load shedding operation
- Longer duration of corrosive conditions
- Loss of passivated layers
- More air intrusion, with O2, CO2
- Rapid startup requirements

Closer control of operation coordinated with lower chloride and sulfate

concentrations can reduce corrosion rates while optimizing generation.
The need for chloride & sulfate measurements

 Cycle chemistry guidelines

8 Comprehensive Cycle Chemistry Guidelines for
Fossil Plants – 1021767 and for Combined
Cycle/HRSG's – 3002001381
8 "Chloride is core parameter, should be monitored
8 EPRI Limits < 2ppb chloride & sulfate
8 2 ppb chloride and sulfate limits for steam,
although not usually measured
8 "The most common corrosive deposits
[in turbines] are salts of chloride and sulfate".
- VGB (updates under consideration)
 Turbine warranties

Cation conductivity vs. anion concentration
Anion limits
Cation conductivity [µS/cm at 25 °C] 2 to 5 ppb

Cation conductivity limits

0.15 to 0.3 µS/cm

Adapted from VGB & Peter Jensen,

PPChem 2000, 2(1), 32

Cation conductivity vs. anion concentration

Cation Conductivity (µS/cm at 25 oC)

Anion 0.15 0.2 0.3 0.5
Chloride, ppb 12 17 25 43
Sulfate, ppb 14 22 33 57

 Guidelines for max. steam cation conductivity: 0.15 to 0.30 µS/cm

 Guidelines for max. steam chloride and sulfate concentrations: <2 ppb

 YET…. chloride and sulfate are not typically monitored because current
measurement equipment is too expensive to acquire and maintain

Cation conductivity limits are inadequate to ensure compliance with anion

steam guidelines and turbine warranty requirements
Microcapillary electrophoresis principle

Electrophoresis: the use of an electric field to separate

particles or ions in an electrolyte based on their mobilities
 The microcapillary dimensions boost sensitivity at low
 Measurement is performed on an automatically introduced
sample for semi-continuous operation.
 Detection is by conductivity.
 Readout is direct ppb concentration.

Microcapillary electrophoresis

 Voltage separates ions based on their size to charge ratio (mobility).

 Confinement within a small capillary enhances separation and sensitivity.
 Separated ions pass a conductivity cell which senses the concentration of
each ion.
MCE Cartridge

Sample Ions

Voltage Applied
MCE Cartridge implementation
Setup for Measurement
 Microchip wells are flushed with background electrolyte buffer and with
sample & internal standard.
 High voltage is applied to load the capillary channels.
Sample & Internal

kV, µA

 Background Electrolyte Buffer: media to enable ionic transport through the

capillary and past the conductivity sensor
 Internal Standard: known concentration solution
MCE Cartridge implementation
 The high voltage is briefly changed across the measurement
channel, pushing a small volume of sample & internal standard into
the buffer channel for analysis.

kV, µA

MCE Cartridge implementation
 To produce separation, the high voltage across the buffer channel
causes ions to move at different speeds based on mobility.

kV, µA

MCE Cartridge implementation
10 µg/L
 As each ion plug is measured, the 12 µg/L
Nitrate Sulfate

corresponding peak represents its 10 µg/L

Chloride 23 µg/L Internal
concentration. Standard

kV, µA

Typical results
Analyzer display
12 µg/L 10 µg/L
Nitrate Sulfate
10 µg/L
Chloride 23 µg/L Internal

 Internal analysis measures conductivity peaks for each ion.

 Each peak is compared to the Internal Standard peak for
 The amount of chloride and sulfate is then displayed on the screen in
 High alarm for chloride and sulfate in sample could be set to 3 ppb
MCE Cartridge

3000CS Analyzer

Removable Cartridge Tray Cartridge

Internal Use Only - CONFIDENTIAL
3000CS Analyzer Components


Temperature controlled
enclosure housing:
• 3 pumps
3 way valve • Mixer
(behind panel) • cartridge

Calibration or
Background Electrolyte
Verification Solution or
GRAB Sample Bottle

Internal Standard

Internal Use Only - CONFIDENTIAL
3000CS Analyzer Specifications
 Measurement: Consumables:
- Species: Chloride, Sulfate - Replacement of cartridge every 2
- Measurement Range: 0 - 500 ppb, limit of months
detection: 0.5ppb - Replenishment of reagents
- Periodic calibration/verification with
- Accuracy: standard solutions
8 Chloride: ± 5% of reading ±0.5 ppb,
typical Service :
8 Sulfate: ± 5% of reading ±1 ppb, typical - PM every six months
- Update time: range 15-90 min (adjustable)

- Fine Pre-Filtering required: No
- Temperature: 10 - 45 °C
- Pressure: 7 - 100 psig
- External multi-stream sequencing compatible
- Ambient temperature: 10 - 40 °C
- Ambient humidity: 10 – 70%
- Output signals: 0/4-20 mA for each parameter

Internal Use Only - CONFIDENTIAL
Summary 32

FGD Wet Stator Cooling
C DO pH Cooling
C CC Na Si DCC Tower
IC pH pH C or IC

Boiler Condenser C pH ORP DO Na Si TOC

pH C
Scrubber Preheaters/ DCC CS RO/DI Makeup
blowdown deaerators Condensate water treatment
C CC pH DO DCC polisher CC
DI Regen. &
RO Cleaning
Coal Pile Boiler
Cooling Tower Waste
Runoff Blowdown, Cleaning
pH pH IC Blowdown
Wastewater Treatment
C = specific conductivity DO = dissolved oxygen Na = sodium
CC = cation (acid) conductivity ORP = redox Si = silica
IC = inductive conductivity pH = pH TOC = total organic carbon
DCC = degased cation conductivity CS = chloride / sulfate

For internal use - Confidential