Analyser S

WELCOME TO ANALYSER
TRAINING PROGRAM
Yokogawa India Limited

WELCOME
Date: 11 July 2006
YOKOGAWA INDIA LIMITED

Analyser Product Portfolio
pH
ZIRCONIA
CONDUCTIVITY
ANALYSER
PRODUCTS
DO
OTHER
LIQUID DUST
ANALYSERS GAS DENSITY
YOKOGAWA INDIA LIMITED Page.2

Analyser System Portfolio
CEMS
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YOKOGAWA ANALYSERS
LIQUID GAS
pH ANALYSER ZIRCONIA OXYGEN
REDOX ANALYSER ANALYSER
ZIRCONIA HUMIDITY ANALYSER
CONDUCTIVITY
ANALYSERS GAS DENSITY METER
DUAL COND ANALYSER CEMS (NO, SO2, CO, CO2
INDUCTIVE COND ETC)
ANALYSER
DISSOLVED OXYGEN
ANALYSER
LIQUID DENSITY ANALYSER

Why pH is monitored?
The water flowing through the piping and components

in plants should be maintained.
If it gets acidic then it can cause corrosion .
If it is Highly alkaline then it may cause scaling.
Hence it is very essential to have pH checks at some
locations in the flow circuit.
Typical pH Analysis points :-

Boiler water, Economizer inlet or feed water.

Why Conductivity is monitored ?
This is used to measure the dissolved salts
/impurities in water.
Thus, conductivity is directly proportional to the
amount of impurities in the liquid.
Conductivity can shoot up if the water comes in
contact with atmosphere. So CO₂ and other gases
dissolve in water and can make the water more
conductive .
Leakages /plant malfunctioning in different
locations can be detected with the help of
conductivity analysers.
Typical Conductivity Analysis points :-

Boiler water, feed water, economizer
inlet,Superheated steam,Saturated steam,DM
water, CEP Discharge,Condensate polishing unit.

Why Dissolved Oxygen is monitored?
Oxygen gets dissolved in water wherever there are leakages
and low atmospheric pressure.
This leads to formation of iron oxides and leads to rusting of
components, feed water tubes and piping network. It also
forms sludge
Dissolved oxygen also promotes electrolytic action between
dissimilar metals and can cause leakages at joints and
gaskets.
Hence to assure proper system protection it is essentials to
monitor Dissolved oxygen at following places.
Typical DO Analysis points :-

De-aerator outlet :- To check the de-aerator performance
De-aerator inlet :- To monitor hydrazine performance in
condensate.
Boiler water,feed water :- To protect tubing.As per DO
level, Hydrazine is dosed.
CEP Discharge :-Since Oxygen can also be introduced
through make up water.

pH

Basics - pH
pH = Activity of Hydrogen ions which defines the

character of a solution
Formula is pH = -log10 [H+]
pH gives an indication of the degree of Acidity or
Alkalinity of aqueous solutions.
Scale of pH is 0 – 14 pH
Ratio of H+ ions and OH- ions is equal then the pH is 7.
pH = pOH = 7
More Positive ions = More Acid
Less Positive ions = More Alkaline
pH is a dilute solution measurement.

pH and some common solutions
Acid - 4%HCl
0
0.4%HCl 1
0.04%HCl 2
0.004%HCl 3 Coca-Cola
4 Tomato Juice
Beer
5
Cheese
6
Milk
Neutral - pure water 7
8
Gin
9
10
Liquid soap
11
12 Washing Soda
13
Alkaline - 4% NaOH 14
pH

Measuring the pH value
Colorometric pH measurement
– pH value is based on the pH dependence of color
change
– Example LITMUS paper color changes to RED
when a solution is ACID and changes to BLUE
when a solution is alkaline
Potentiometric pH measurement
– Explained by NERNST’s law
– Potential difference occurs between metal object
and a solution containing ions, when object
immersed in the solution

Components of pH measurement system
Glass Electrode
Reference Electrode
Temperature sensor
Liquid Earth
Ζin > 10 Ω
13
A
A-B
Ζin > 10 Ω
13

Basics – Glass Electrode
Membrane made from special glass formulation

(Glass Bulb) – Responsive to Hydrogen ions.
A chemical reaction between sample &
membrane surface – generate electrical
potential dependent of pH.
Ion exchange process develops a charge on the
membrane surface.
Net effect is voltage buildup across the
membrane is proportional to H+ ions in the
sample.

Basics – Reference Electrode
This provides return path for electrical circuit.

It is essential that reference electrode potential
should be very stable.
Silver Chloride type reference electrodes are
commonly used.
Electrolyte from the reference electrode seeps out
through ceramic junction.
This makes electrical connection between reference
element & sample.
Generally KCL is filled in reference electrode as it is
chemically inert.

The pH glass electrode, how does it work?
pH
Reference Electrode Glass Electrode
H+
H+ pH 7 buffer H+
H+ H+ H+
H+ H+ H+
H+ H+
H+ H+
Ceramic Junction Process fluid H+
H+
H+ H+ H+

Electrode Construction
Et
Et
E4 E3
Electrolyte
R Electrolyte
R
E2
E5
Membrane R
Diaphragm
R E1
Et = E1+E2+E3+E4+E5
E5 E4 E1 E3 E2

pH sensitivity with temperature
As the temp increases, slope of the electrode pair
(mV/pH) also increases.
600
400 25°C
200 10°C
50°C
0 pH
-200 0 2 4 6 8 10 12 14
-400
-600 mV
Wide Range of pH sensors

Bellomatic Reference Electrode

The Bellomatic Principle
Process pressure + spring

force of bellow
Process Pressure

FU20 Combined Sensor (Four - in - One)
PTFE junctions
Reference
Glass (pH)
Temperature
ORP / Liquid earth

Flow Assembly Mounting

FU20 Mounting Examples
Using standard pipe fittings in PVC from your local

plumbing supplier or hardware store.

Possible Troubles in pH – Due to….
GLC – Ground Loop Current
Increase in impedance due to

depletion of Reference Junction,
Poisoning / Coating on Electrodes
Breakage / crack in the sensor

Troubles caused by Ground loop Currents
Different connections to
ground ask for ground
loop currents
Galvanic isolation is
minimum requirement
GLC causes pH-
errors
GLC destroys
Reference Elements

Differential Amplifiers – Protection from GLC
Traditional pH meters are

grounded via reference electrode.
Common mode voltage causes
easily ground loop currents
through the reference electrode
In many applications (electrolysis,
pure water, simple electrode
cabling) electrodes are eaten by
ground loop currents
Differential amplifiers offer
lightning arrester for GLC

Why impedance monitoring ?
60-80% of measuring problems is caused by plugged,

poisoned, depleted reference junctions
The impedance of the junction is THE indicator for junction

troubles
Glass electrodes are sensitive for breakage. A broken

sensor gives “dangerous” signal.
The impedance of the Glass indicates integrity of the

sensor

Why Dynamic Sensor Check ?
In many applications sensors need regular cleaning
Chemical cleaning is most effective way to remove

scaling
Good dynamic response guarantees clean and good pH

sensors
Dynamic sensor check gives feedback on cleaning

resulting in more effective use of chemicals and in
cleaner electrodes

INTEGRATED ALARM AND CONTROL
Automatic wash cleaner
BURN-OUT : UP OR
DOWN SCALE
According to Namur
Recommendation 43

Automatic Wash Function
Contact can be chosen to operate

metering pump or solenoid.
Timer is used to determine
frequency and duration of the
washing action plus the duration
of HOLD
HOLD is chosen to be “last value”
or “fixed mA” .

YOKOGAWA OPENS UP TO THE WHOLE WORLD
E+H
AMAGRUSS
INGOLD
DANFOSS
YOKOGAWA
ANTIMONY
TBI
YOKOGAWA
YOKOGAWA
PFAUDLER

80 years of experience
Operator interface
Improved housing
Backlight
Recorder
Life time prediction
µP based
Sensordiagnostics
Digital
IC based
EXAxT series
EXA series New Millenium

transistor
1990ies
Sigma series
1980ies
Eltran series
1970ies
Industrial pH
analyzer 1957

Models of pH Converters
Simulator

Calibration of pH systems Hints
How often ? once per month !

How often are sensors cleaned ? Depends on
application !
How do we calibrate ? Using fresh NIST pH
buffer solutions 4.01 and 6.86 pH
How do we use laboratory analysis ? Only for
validation records

ORP

Oxidation – Reduction Potential (ORP)
ORP stands for Oxidation-Reduction potential,
It is a measure, in milli-volts, of the tendency of a chemical

substance to oxidize or reduce another chemical substance.
Oxidation is the loss of electrons by an atom, molecule, or ion.

Familiar examples are iron rusting
Reduction is the net gain of electrons by an atom, molecule, or

ion.
Oxidation reactions are always accompanied by reduction

reactions. The electrons lost in oxidation must have another
substance as a destination, and the electrons gained in reduction
reactions have to come from a source.

REDOX examples
Acid Permanganate solution is strongly oxidizing:
it strongly attracts electrons from the REDOX
electrode: the REDOX potential is highly positive
Sulphite solutions are strongly reducing. It
pushes electrons into the electrode. The REDOX
potential is strongly negative
+ -

ORP MEASUREMENT
When a chemically inactive metal electrode is in solution

where an oxidation-reduction reaction is taking place,
electric potential appears at the electrode. This potential is
called the oxidation-reduction potential.

ORP APPLICATIONS
Monitoring and Controlling Oxidation-Reduction

reactions. Basically to find out the reaction is
complete.
Examples: Cyanide destruction, de-chlorination,
chromate reduction, hypo chlorite bleach
production, etc
Concentration Measurement. Example: chlorine in
water
Standardized approach to water dis-infection for
harvest and post-harvest handling.
Example: Food processing, Shipping

Conductivity
Contact Type

What is Conductivity
Conductivity measures how well electrical

signal passes through liquid.
The unit is Siemens, m Siemens, µ Siemens
The Multiplier is the cell constant: l/O
The result is Specific Conductivity in mS/cm

What is specific conductivity ?
Specific conductivity
– Conductivity value of a liquid column with a l= 1 m (1cm)
A= m² (1cm²)
– Cell constant x Conductance (S/cm ~ mhos/cm)
Κ = G x L/A (S/cm)
– Κ = specific conductivity
– G = conductivity in Siemens
– L = Length of the liquid column in m (or cm)
– A = surface area in m² (or cm²)
Conductivity = number of ions in the solution

(also called concentration)

What is the cell constant ?
Cell constant 1.0 cm-¹ = 1cm x 1cm x 1cm
Conductivity means nothing without
interpretation
Factor depends on
– size of the electrode plates
– distance apart
C = L/A (1/cm)
– L = distance
– A= Area
A potential is applied across the plates -

current is measured
U=I x R ~ R=U/I (ohm)

Conductivity of Familiar Liquids
.01 .1 1 10 100 1000 10 100 1

µS/cm µS/cm µS/cm µS/cm µS/cm µS/cm mS/cm mS/cm S/cm
Ultrapure Tap Water

water Beer
Milk
Good Quality
Distilled or
Deionized Water
Sea Water 30%

H2SO4

Basic Principle
Voltage
Meter
Source
Cathode Anode
- ++
- -- - +
+ + ++
- -- + - - +
+
+ - +-
I
Ions G= Siemens / cm (formally Mho)
Ra
Where G is the Conductivity in Siemens /cm
I is the length of the sample in cm
a is the cross-sectional area in cm2
R is the sample resistance in ohms.

Effect of temperature
Conductivity data is usually reported at 250C

Higher temperatures make the ions move faster and
increase the conductivity measured.
The size of this effect depends on the actual
process.
All conductivity sensors contain a RTD element to
measure temperature and compensate the raw
conductivity data.

Temperature compensation
Conductivity will increase

with temperature
Slope = ∆ conductivity / °C
Examples
– Acids 1.0 - 1.6% / °C
– Bases 1.8 - 2.2 % / °C
– Salts 2.2 - 3.0 % / °C
– Fresh Water 2.0 % / °C

Effect of Polarization
What happens when
polarization takes place :
– Voltage across steering
electrodes decreases
– Current through solution
will decrease
– The measured voltage
across measuring electrode
decrease Movement of Ions towards electrodes
– Produces error with respect

to reference voltage
– Makes capacitance effect
– Capacitors charged upto the
applied voltage, which
reduces current practically
to ZERO
Polarization Resistance Vs
Liquid Column resistance

Preventing Polarization Effect
Applying AC voltage to the electrodes

– Polarization phenomenon reduced due to reversal of polarity
Selecting the correct cell constant
– As cell constant is obtained from size of electrodes,
polarization reduces if the size is appropriate
Adjusting the frequency according to cell signal
– See next
Applying 4 – Electrode Measuring Principle
– Voltage across steering electrodes is corrected until the
current through the cell generates a voltage across the
measuring electrodes which is equal to the reference
Voltage

Frequency control
It is standard to change
frequency between low and high
measurements
Low conductivity = high
resistance & big capacitive effect
so low frequency
High conductivity = low
resistance & risk of polarisation
so high frequency
EXA does this automatically in High conductivity
response to measuring signal. Low conductivity Higher frequency
The signal is continuously Low frequency
monitored and adjusted to the

best frequency.

Conductivity versus Conc. Graphs
Conductivity rises linearly with concentration in dilute

solutions
Ions interfere with one another in concentrated solutions so
conductivity may stop rising or actually fall.

Conductivity Analyser Family

Where Conductivity Analysers Used?
Power Generation:
Water/steam/condensate cycle.
Semiconductor industry: water quality,
etching fluids, water treatment.
Pharmaceutical industry: injection water,
USP
Chemical industry: concentration
measurements, production quality control,
water treatment
Food (CIP), Pulp & Paper (condensate),
Steel (etching fluids) Sugar (Briggs)

Model of Conductivity Converters
Simulator

Inductive
Conductivity

Inductive conductivity
Method
– A current is induced in the liquid.
– Magnitude of the current
depends on the conductivity of
the Liquid
Sensor
– pair of transformers with a
common turn.
The liquid forms one winding:

– secondary for the 1st transformer
– primary for the 2nd transformer
How does it work ?
Receive coil Drive coil
Transmitter supplies reference voltage
Generates magnetic field in drive coil
and 2nd winding (the solution)
This induces a current in the liquid ~
conductivity
Current will induce magnetic field in
receive coil
Output voltage = dependent on
current flowing through the solution

Inductive - Principle of Operation
PICKUP
The Induced Current is
Input Voltage
To Coil
Dependent on the
Conductivity of the Sample
COIL
Sample
(Liquid Loop)
DRIVE
COIL
DRIVE PICK-UP
COIL COIL
Cores are made of Super Malloy Sample

a highly refined & specially (Liquid Loop)
processed 80% Nickel - Iron PROCESS
Alloy in 0.002 inch thickness.It has high
permeability and low losses FLUID
Acts as a single turn winding

Cell constant versus Installation factor
Cell constant is determined by dimensions

– all conductance within the sensor
Installation factor is size, & mounting too

– influence from the pipe walls or tank

Contact or Inductive Conductivity
Contact Inductive
High accuracy at low High accuracy at high
conductivity by shielded conductivity by absence of
construction polarization
Compact sensor with low Compact sensor at high
constant constant
Easy mounting for shielded Calibration needed in compact
cells installations
Common use in Chemical Not used for electrolyte
Industry measurements
Contact for Inductive for the rough
[[ultra]pure] water applications

Contact or Inductive Conductivity
Contact Type Inductive Type

Model of Inductive Conductivity Converters
Simulator

Dissolved
Oxygen

Theory
Amount of Oxygen
that a given
volume of water
can hold is a
function of:
1. The pressure the

atmospheric
oxygen is exerting
at the air-water
interface….

Theory…Continued
2. The
temperature of
the water.
3. The amount of
other substances
dissolved in the
water.

Effect of Partial Pressure
Water in contact
with air will absorb
air (O2)
…until the pressure
at air-water interface
is equal…
Said to be saturated
- about 5 to 10 parts
of oxygen to one
million parts of water

Effect of Temperature
Pot of boiling water…

bubbles form on
bottom & sides of
pot…
number & size of
bubbles increase
with temperature….
These are air
bubbles that have
been dissolved in
water.

Basic Measurement Techniques:
I. Electrode System
Electrode system separated from the sample stream
by semi-permeable membrane, which permits DO in
sample to pass through to the electrode system, but
prevents passage of liquids & ionic fluids.
An electrode system where DO reacts at the
cathode producing a measurable
electrochemical effect.
Effect can be galvanic (ability to conduct an
electrical current), polarographic
(electrochemical), or potentiometric
(measurement of voltages).

Basic Measurement Techniques
II. Winkler Method

Winkler method (azide
modification) SM 4500-OC
(or ASTM method D88-
92(A) or another Winkler
method promulgated by
the USEPA.
Measurement by adding
Chemical reagents to the
sample & effect of reaction
gives the DO value

Dissolved Oxygen Measurement
Current meter
Lead Anode Silver Cathode
Water
Polymer membrane
permeable for gases
Oxygen dissolves in water

The Oxygen molecules move through the membrane
The Oxygen is consumed by the Cathode:
O2 + 2 H2O + 4e === 4 OH -
Simultaneous reaction at the Anode:
2Pb + 4OH- === 2PbO + 2 H2O + 4e
The electrons cause electrical current !
The Oxygen concentration inside remains zero
What you need….

– Polarographic or Galvanic sensor
– An Electronics capable to make…
– Temperature Compensation
– Pressure Compensation
– Salinity Compensation

What is Polarographic
Polargraphic cell has two noble-metal
electrodes and requires a polarizing voltage
to reduce the oxygen.
The dissolved oxygen in the sample
diffuses through the membrane into the
electrolyte, which usually is an aqueous
KCI solution.
If there is a constant polarizing voltage
across the electrodes, the oxygen is
reduced at the cathode and the resulting
current flow is directly proportional to the
oxygen content of the electrolyte.
The oxidation-reduction reactions, in the
case of a gold-silver cell with KCI
electrolyte, are as follows:
– At the gold cathode: O5 + 2H2O + 4
electrons 4(OH-)
At the silver anode: 4Ag + 4(Cl-) + AgCl + 4

electrons

What is Galvanic
Galvanic cells consist of an electrolyte and two
electrodes
Oxygen content of the electrolyte is brought
into equilibrium with that of the sample.
Electrodes are polarized, which causes
electrochemical reactions to take place when
oxygen contacts the electrodes.
Cathode reduces the oxygen into hydroxide,
thus releasing four electrons for each molecule
of oxygen.
These electrons cause a current flow through
the electrolyte, the magnitude of which is in
proportion to the oxygen concentration in the
electrolyte.

Why Temperature compensation
Current = Diffusion
rate depends on
current as function of temp
temperature. 1.4
µA1.2
1
0.8
25 micron
50 micron
0.6
0.4
0.2
0
0 5 10 15 20 25 30

Why Pressure compensation
The solubility of Oxygen

depends on Pressure
solubility as function of temp
The Pressure varies 15
with weather and 14 ppm
altitude 13 mg/l
12
11
atm.
10
1750 m
9
8
7
6
5
0 10 20 30 40 50 temp

Why Salinity compensation
The solubility of
Oxygen depends on solubility as function of salinity
Salinity 15
14 ppm
13 mg/l
12
11
Pure
10
30 ppt
9
8
7
6
5
0 10 20 30 40 50 temp

Why AIR and WATER calibration
AIR calibration is easy and reliable

WET calibration is “common
practice” but only with complete
saturation it is accurate
ZERO calibration in Sulphite
solution is possible but is not
recommended
AIR calibration is best done with
sensor in empty bucket for faster
stabilisation

Zirconia Oxygen

O2 Applications & users?
Who measures Oxygen?

Any one who needs to monitor and/or control their combustion process.
Power utilities
Pulp and paper mills
Steel mills
Refineries
Chemical Plants
Waste incinerators
Package boiler users
Cement Plant (kilns)

Why Oxygen is monitored?
To save energy and cost incurred in operation

of boilers
To protect the environment from Pollution

O2 Theory
Heat What is Combustion?

Air Fuel Flue Gas
H 2 (hydrogen) H 2 O (water)
O2 + CO 2 (carbon dioxide) Combustion is the combination
C (carbon)
of fuel and air with heat produced
COMPLETE and carried by the mass of flue gas
generated.
Heat Flue Gas After combustion, if O2 content in

the flue gas is
Air Fuel H 2O (water)
CO 2 (carbon dioxide) O2% < 1% means “Combustion is
H 2(hydrogen) proper”
O2 + CO (carbon monoxide)
C (carbon)
H 2 (hydrogen)
C (carbon) O2% > 5% means “Wastage of
heat, Uneven combustion inside
INCOMPLETE Aldehydes the Boiler and unwanted
reactions”

How combustion is controlled?
Optimum Combustion Zone
Heat Efficiency
Heat Loss
Combustion Efficiency
Energy loss - due
to incomplete
combustion
(unburned fuel)
Heat loss - dissipated
from the stack
1.10
1.0 1.02
MIN
POLL
Smokey UTION NOx and SOx increase
Low Excess High Excess Air Ratios

Air Ratios
Insufficient Air

Where are we measuring ?
Probe
Primary
Super-heater
Economizer Probe Protector
Burners
to Stack
O2 Probe
Placement
Air Pre-heater
Filter
Combustion Zone

Where are we measuring ?
Measure O2 here!
Air
BURNING Gases
Fuel

Zirconia Oxide – Cell Theory
Platinum Electrode
Zirconia
Sample Gas
Oxygen Partial Pressure = Px
O2
O2-
O2-
Reference Gas
Oxygen Partial Pressure = PA

Zirconia Oxide – Cell Theory
Platinum Electrode
Zirconia
Sample Gas
Oxygen Partial Pressure = Px
O2
O2-
O2-
Reference Gas
Oxygen Partial Pressure = PA
Nernst Equation: PX
Electromotive Force E (mV) = -50.74 log P
A

Electrical Equations
Reaction at the Platinum Electrodes
Reference Side (+) : O2 + 4e- 2O2-
Measuring Side (-): 2O2- O2 + 4e-
Nernst Equation:
E (volts) = RT 1n PX = -2.3026 RT log PX
nF PA Nf PA
R = Gas Constant (8.31 joules/mol ºK)

T = Absolute Temperature (ºK) [ ºK = 273.15 + ºC ]
n = Electrons (4)
F = Faraday’s Constant ( 9.64 x 104 coulomb/mol )
PX = Partial Pressure of O2 on Sample Side of Cell
PA = Partial Pressure of O2 on Reference Side of Cell
ZO21D probe temperature is 750 ºC (1,023.15 ºK), so substituting known values for
variables gives us:
E (mV) = -50.74 log PX

PA
O2 Concentration Vs Milli Volt
Oxygen Concentration and Cell EMF

(PA = Partial Pressure of O2, Reference)
100
E (millivolts)
75
E
=
50
-5
0.
74
lo
g
(XP
25
/AP
)
0
20.9
0.2 1.0 10 100
O2 concentration

Components Zirconia O2 Analyser
Zirconia Probe Consists of
– Zirconia Oxide Cell – To get EMF according
to O2 concentration
– Heater – To heat
– Thermocouple – To Monitor the cell
temperature
– CJC – Cold Junction Compensation
Electronic – Converter

Zirconia Sensor & Probe Construction
Zirconia Cell Detector Construction

360º Contact of Process Gas
Nichrome Wire Coil
Platinum Electrode
Originally Manufactured
Features:
• Platinum electrode originally
manufactured Solutions:
• Special coating protection of • Prolongs sensor life
platinum electrode • Prevents sensor deterioration
• Lead-less sensor • Eliminates disconnection; High
reliability

Detector
Field replaceable sensor

Optional Inconel bolts for 600< T < 700 C

Reference Air (natural convection)
Process Gas Ambient Air
Cal Tube Reference Air

Zirconia Cell
. ..
Reference Air
Heater
Calibration Gas Inlet
Reference Air Tube Piped Reference Air

Rebuildable detector
First remove terminal

box or integral
converter
Then remove gas-block
Remove ring-nut and pull out the heater strut assembly

Single Point O2 - Basic System
Converter
||||||||||||||||||||||||||||||
0 10
M EAS
M AINT
ALM
FAIL
6.8 % O2
EXA OX Y
Auto-Cal Wire (3)

Signal Wire (6)
Heater Wire (2)
Probe
Instrument Air
AC1 Zero Gas
.025” Tubing

High Temperature Zirconia Probe
Instrument Air
Supply
Regulator &
Guage
>1200 deg C

High Temperature Zirconia Probe
High temperature adaptors
available for temperatures
above 700 ° C up to 1400 °
C
Auxiliary air ejector also
available to suck the flue gas
up to the sensor in case
there is negative pressure in
the furnace.
Blowback arrangement
option also available to clean
the probe

History of Yokogawa Zirconia Oxygen Analyzer
1st Generation (1970s) 3rd Generation (1990s)

Analog Type (ZO6C) Multifunction (ZA8C)
2nd Generation (1980s)

Microprocessor-based
(ZO21C)

4th Generation Zirconia Oxygen Analyzer
1st Generation (1970s)

Analog Type (ZO6C)
3rd Generation (1990s)
Multifunction (ZA8C)
2nd
Generation
(1980s)
Micro-
processor-
based
(ZO21C)

ZR Series Zirconia Oxygen Analyzer

Humidity

Humidity Measurement
Vol% H2O = 100 - Vol % O2
0.21
STEAM
0 100 %
H2O
Water
Gas Composition
79%
N2
Nitrogen
21%
O2
Oxygen
0
100 %

Gas Density

Principle of Thermal Conductivity Meter
Resistance of heated wire JR
JR = KC x ( I2 / K ) KC is constant
I
Fixed
Gas resistor
G
Fixed
Reference resistor
resistor I ( ampere) : constant
Ambient temperature : constant

Gas Density Meter
Explosion proof Detector GD40 General purpose

converter GD402R converter
GD402G
Rainproof for outdoor

Rainproof for outdoor use; intrinsically safe Rainproof for
use; flameproof and flameproof outdoor use ( IP65 /
construction construction NEMA4X)

Principle of Gas Density Meter
Resonator (thin wall)
Detector Piezo-electric
Gas flow actuator
Multi-mode oscillation
system

GD402 Gas Density Analyser
Uses Multi-Mode Oscillation Technique
Axial Circumferential
Oscillation Oscillation
Both oscillation modes are excited at 2 and 6 kHz

Sensor structure
O ring Temperature sensor

O ring
Gas Out
O ring Resonator O ring

Gas In

Operating principle
Phenomena: Resonating Frequency of a Thin

walled cylinder varies according to the density
of given fluid/gas media
If a cylinder vibrates in a fluid / gas media,
the media became internal load to the
cylinder. This results the change in resonant
frequency.
Since the change in frequency is function of
density, density can be by measuring the
resonant frequency

Linearity of calorie. Specific gravity versus thermal conductivity
Thermal conductivity (Air = 1.00)

Calorie ( kcal /m )
Thermal conductivity calorie

non linear
Specific gravity
linear
Specific gravity (Air = 1.00)

Influencing Factors
Temperature: To be measured &

compensated.
Pressure: To be measured & compensated.
External vibration: In Yokogawa case, this is
prevented by sensor construction

Temperature Effect on Gas Density Meter
1.300
1300 70
1g / m3 / 10 ºC or less 60
60
1295
1.295 50
Temperature (ºC)
40
40
Density (kg / m3)
1.290
1290 10 ºC change 30
20
20
1285
1.285
1280
1.280 Density 0
0
Oven temperature -10

1275
1.275 -20
-20
00 5
5 10
10 15
15 20
20 25
25 30
30 35
35 40
40 45
45 50
50 55
55 60
60
Time (hours)

Vibration Effect on Gas Density Meter
1.300
Density (kg / m3)

0.3 g / m3
1.295
1.290
1.285
1.280
0.0 65.3 140.7 216.1 291.5 366.9 442.3 Oscillation
frequency (Hz)
212
10
245 255
229
Acceleration
(G)
73 175 212
0
0 Frequency (Hz) 500

Hydrogen Purity Meter
H2 distribution piping
Collector
Turbine side side Air out
Hydrogen cooled generator
CO2 line
Filter Emergency Filter
out vent
GD40
Flow meter
Filter GD402
Pressure regulating
valve
Regulator Regulator
H2 gas cylinders CO2 gas cylinders

Replacement Meter
H2 in AIR 1. H2 in CO2
Range : 85 ~ 100 % H2 2. AIR in CO2
Range 0 ~ 100 % H2
0 ~ 100 % AIR
Hydrogen purity
100%
H2 100%
1. H2 CO2
CO2
85% 100%
Basically Hydrogen purity is AIR

approx. 100 %. Actual
100%
2. CO2 AIR
concentration is lower by CO2
leakage of air. 100%

Replacement Meter Configuration
Generator Pressure
Vent Transmitter
Calibration gas
CO2
Flow-meter
H2
Valve

Measurement range and gas concentration
1.977
Density
kg/m3
1.293
0.090
H2 Air CO2
100% 100% 100%
Gas concentration
GD402 with Hydrogen purity and replacement

H2 100% CO2 100%
Calibration
0.090 kg/m3 Air 100% 1.9 77 kg/m3
Air 0%
1st output
H2 100% Air in CO2 H2 0%
2nd output
H2 in CO2

7 measurements by Gas Density meter
SENSOR
Actual density
frequency pressure
d kg/m3
temperature
(t ºC, P kPa)
Gas density at standard conditions Compensated density

do kg/m3 d' kg/m3
(0 ºC, 98 kPa) (t ºC, P kPa)
Molecular Total Gas Specific

weight heating concentration gravity
capacity
M P vol% S
Q J/m3
do − dz S=do/1.2928
M=22.414 x do P= × (Ps − Pz ) + P2
ds − dz
do − dz
Q = Qs − × (Qs − Qz )
ds − dz

Superiority in Applications
1. City gas : LPG calorie control
Natural gas calorie control
2. Power station : Hydrogen purity
Replacement meter for
hydrogen cooled turbine
3. Refinery : Hydro-carbon recycle plant
Density control of refining
off-gas

SWAS FOR POWER PLANTS

Requirement of Steam & Water Quality Analysis
Water Quality Management – The most important factor.

Main aim of water quality management is to get better quality of
water and steam
Therefore analysis is required to measure and control impurities and
additives
In the initial years lab analyses was done, but was not accurate
With the help of SWAS, first impurities are measured at various
points and then corrective action is taken
Following measurements are done with the help of SWAS package
– pH
– Conductivity
– Dissolved oxygen
– Silica
– Sodium
– Hydrazine

pH Measurement
Steam used for power generation should be ultra pure

To achieve this purest form of water required
pH measurement indicates alkalinity or acidity of this
water
In general ph value of feed water is kept at slightly
alkaline level
Helps in preventing the corrosion of pipe & other
equipments

Conductivity Measurement
It gives indication of contamination of water/steam with

any kind of salts which are added due to leakages
Specific & cation conductivity is measured
Specific conductivity measures all ions in the solutions
Cation conductivity is measured after cation column
Contains hydrogen ion exchange resin. Which removes
ammonia and amines
Very good method of checking the leakages in the circuit

Cause of corrosion & leakages

Measured in ppb range

Silica Measurement
To achieve this purest form of water required

Silica gets deposited on the blades
With high pressure solubility of silica increases
Due to deposition on blades loss of efficiency
Measured in ppm range

Sodium Measurement
Major cause of corrosion in turbines


Hydrazine Measurement
Hydrazine is used as additive

Hydrazine is an oxygen scavenger

Ex-Situ Measurement
Samples are at high temperature & Pressure

Sample conditioning required to bring down
the temperature & pressure at desired level
SWAS package has two types of panels:
Wet panel
Dry panel

Wet Panel
Sample coming from different points are fed

into this panel
Contains sample conditioning components like
IV’s, Filter, Cooler, PRV, SOV’s Temperature,
Switch, Pressure & Temperature Gauges,
Rotameters etc.
Sensor in the same panel
Output of sensor goes to dry panel

Wet Panel (Frontal & Rear View)

Wet Panel (Frontal & Rear View)

Flow Schematic Diagram for SWAS

Dry Panel
Contains annunciators, indicators,

transmitters etc.
All remote signal goes from this panel to
control room

CEMS

CEMS – An Introduction
Continuous Emission Monitoring System

– Consisting of Gas Components Monitor,
• Carbon Monoxide (CO)
• Sulfur Dioxide (SO2 )
• Nitric Oxdies (NO, NO2 or NOx)
– Flue Gas Flow Monitor
– Dust Monitor
All CEMS must be continuous in operation for the for
measurement data update in every 15 min
All units over 25MWs and new units under 25MWs
that use fuel with a sulfur content greater than
0.05 % by wt. are required measure and report
emissions.

General Terms
FLUE GAS - gases present after something is burned.

Usually includes O2, CO2, H2O. May include NOx, SO₂
PRODUCTS OF COMBUSTION - results of burning, includes

FLUE GAS and particulates.
EXCESS OXYGEN - left over O2 in FLUE GAS
COMBUSTIBLES - gases that will burn (CO, CH4, etc). If in

FLUE GAS, may interfere with EXCESS OXYGEN reading

Why monitor Stack Gas?
Clean Air Act

42 U.S.C. s/s 7401 et seq.. (1970)
The Clean Air act is the comprehensive Federal law that
regulates air emissions from area, stationary and mobile
sources. This law authorizes the U.S. EPA to establish National
Ambient Air Quality Standards (NAAQS) to protect public health
and environment.
environment
U.S. EPA (Environmental Protection Agency)

40 CFR : Code of Federal Regulations - Title 40: Protection
of environment
40 CFR 75:
75 Continuous Emission Monitoring System,
A 128 pages document, Under the "Acid Rain Program", this
code contains the implementation Guidelines, specific provisions
for monitoring emissions and detailed reporting & certification
procedures.

The Analytes
Combustion gases
CO, CO2, SO2, NOX, HCl
Atmospheric gases
O2, O3, CO2, H2
Process gases
H2S, CO2, Cl2

Types of Measurements
Electro Chemical Sensor Based

– Electro Chemical Sensors produces electrical
signals according to the gas components present
Infrared Rays Based

– Uses Infrared Rays absorption principle
– Widely available in 2 techniques – Extraction
Method & In-Situ Method

Why CO measurement is important?
To ensure proper combustion

To avoid Heat Loss
To ensure combustion efficiency

Why SO₂ / NOx measurement is important?
With moisture, it creates – ACID RAIN

Highly Corrosive
Mandatory – Under Pollution Control Act
Unwanted Reaction: Production of Sulfuric
Acid
a. 2SO2 + O2 = 2SO 2SO3
SO3 + H2O = H2SO4
b. NO2 + SO2 + H2O = H2SO4 + NO

Unwanted Reaction: Inter-conversion of
Nitrogen Oxides
a. 2NO + O2 = 2NO2
b. 2NO2 = N2O4

Why SO₂ measurement is important?
Sulfur Dioxide Solubility in Water

100
SO2 Solubility (ml SO2/100 ml H2O)
90
80
70
60
50
40
30
20
10
0
0 10 20 30 40 50 60 70 80 90 100
Temperature (Deg. C)

Coal-fired Thermal Power Plant Typical Flow Chart
Stack
Boiler
Flue Gas Coal

Desulphurizer Bunker
Electrostatic
Precipitator Turbine
Generator
Burner
Coal
F.D.F Mil
Water Treatment
Unloader
ReclaimerStacker r
Calcium Fly Ash
Carbonate
Ash Stock Yard
Pond
Waste Water
Treatment

Methods of Analysis System
IN-SITU method
– The Analyzer with probe directly mounted on the
Stack/Duct
– Analyser (Transmitter & Receiver) mounted across
the Stack/Duct
– Wet measurement basis, at actual process
conditions, but prone to high temperature, dust &
moisture conditions
– Difficult in maintenance (at high location)
– High maintenance cost; frequent cleaning due to
dust/moisture
– Analyzer prone to high temperature & moisture
– High temperature versions (<450 Deg C) are very
costly

Methods of Analysis System
EXTRACTION method
Gas analysis for Emissions or Process Monitoring
involves three steps:
1. Sampling 2. Conditioning 3. Analysis
Samples are typically: Analyzers require samples to be:

• Wet • Dry
• Hot • Cool
• Dirty • Clean

Extraction Method
In EXTRACTION method Sample Conditioning
receives little attention,
But Retain water-soluble analytes (HCl and SO2)
Achieve low final sample dew points (down to -

25oC)
Accept high sample flow rates (up to 25 L/minute)
Resist corrosion (minimal maintenance)
Accommodate nearly any sample (customized)
Eliminate heated sample lines (stack mounting)

Analyzer System
Sample Probe/Process Tap
Location, Installation Details, Probe Design
Pre-Conditioning System
Response Time, Effects on Transport Line,
Sample Return/Disposal
Sample Transport Line
Line Sizing, Pipe/Tube Material, Heat/Cooling of Line,
Installation Requirements
Sample Conditioning System
Flow/Pressure/Temperature Regulation, Sample
Filtration, Response Time, Sample Phase Change
Requirements, Maintenance

Analyzer System…. Continued
Process Analyzer
Measurement, Range, Accuracy/Repeatability,
Response Time, Installation & Maintenance
Requirements
Analyzer Calibration/Validation System
Lab/Grab Sample, Calibration/Reference
Standards, Manual/Automatic, Double Block &
Bleed
Analyzer Shelter
Rack, Cabinet, Open Shelter, Ventilated House
Sample Disposal/Return
Supply/Return Line Lengths, Atmospheric
Vent/Flare/Drain, Back Pressure, Environmental
Emissions

A Typical System
Probe with inside filter
from Location-1 Field
Sample Handling Analyzer Panel
SV1 System-1
SV2
SV3 SV4
NO Cylinder
CO Cylinder
SO2 Cylinder
N2 Cylinder

Sample Handling
System-2
Sample Handling
System-3

Analyser Panel Components - Typical
CO SO2/NO NO2/NO
Analysis PLC for Control & Analyzer Analyzer Converter
Panel Signaling
AV01
BP02
BP01
FM02
P01
SG01
SV01 FM01
SV06
MD01
SV04
SG02 P02
SV02 SV07
SV05
SG02
SV03 SV08

DRYING METHODS
Refrigeration Dryers
Removes the water by condensation but in this
method the water soluble analyte gases dissolve in
the condensate and are removed as well.
Desiccant Dryers
Absorbs water but also absorbs analyte gases
another disadvantage is recurring cost of chemical.
Also if there is any choking in the sample line the
pressure created in the desiccant dryer will cause
chemical spillage .
Permeation Dryers
Removes water due to its molecular size,which also
removes portion of analytes,hence the analysis is
never correct.

DRYING METHODS
Nafion Dryers :
Nafion gas drying is the best method to remove
moisture
As it selectively removes water from gas samples
without removing analytes based on chemical
selectivity and not on size.
It removes moisture down to a dew point of –
15deg.C. because of which the sample gas doesn’t
contain any mist thereby requirement of separate
acid mist filter is eliminated.

Nafion Gas Dryer
♦ No Sample Loss ♦ No Routine Maintenance

♦ Low Sample Dew Point ♦ Corrosion Resistant
♦ Fast Response ♦ No Moving Parts
♦ Continuous Drying ♦ Rugged Construction
♦ Self-Regenerating ♦ Small Size

Nafion Gas Dryer
Using Nafion® GAS DRYERS

• Water is removed very selectively.
• Final dew point is as low as -45oC.
• Drying occurs in a fraction of a second.
• Drying is continuous and self-regenerating.
• Dryers are corrosion-resistant and rugged.
• Dryers require no routine maintenance.
Summary of Dryer Features
• Dries final sample
• More accurate results
• Tolerant of very harsh samples
• No routine maintenance
• Highly reliable
• Easy to operate
Nafion Gas Dryer

Principle of Measurement
Dual Beam

Principle of Measurement
Single Beam

Function of Thermal Flow Sensor

Features of Infrared Analysers
Highly sensitive thermal flow detector which helps in distinguishing and
eliminating cross sensitivity specially measuring CO & CO2 which are
almost in the overlapping region of infrared spectrum.
Single point chopper: Even if the amount of light changes due to
mechanical play,the distribution cell equally divides the amount of light
into two fluxes and as this change occurs simultaneously on the sample
& reference side they are cancelled out in the measuring output and the
effect of noise is eliminated.
IR Light Source: A light source for infrared analyser requires a
sufficient amount of light ,stable & equal light.IR8 analyser has a large
emission area which effectively utilizes the light from rear of the light
source by mirroring the wall of light source chamber .
Optical System: Perfectly balanced optical system thereby reducing the
effect of noise

YOKOGAWA Analysers – Model IR8



IR8 Analyser – Panel View

IR8 / MG8 Analyser – Panel View

IR200 Analyser – Panel View

Typical Emission Monitoring in a Power Plant
Combustion Control Plant Control Emission Control
Zirconia
O2
Transformer Dust
Heater
CO,
NO
SO2,
SO2 NOx
, CO,
De Flue Gas CO2,
NOx desulphu O2,
etc.
Ammonia -risation
Turbine
Generator
Dust
NO,
NH3
Fuel and
Air Supply
Temperature
Stack
Boiler Ash Dust

Filter
ssssssssss
AAAAAAAA
Cooling Tower
Heat Exchanger

Infrared Applications
Blast furnace: CO, CO2 Ceramic sintering

Electric furnace: CO, CO2 oven: CO
Coke oven: CO, CO2 Lime Kiln: CO, CO2
Ammonia plant:
CO, CO2
Boiler, Heat Ethylene plant:
furnace, CO, C2H4
Sintering oven, Petrochemical
plant: CO2,C3H6
Cement Kiln, : Gas plant: CO, CO2
O2,CO,
CO2, NOx
Plant carbon, Apple

storage, Rice storage, Building Air conditioning:
CO2
Brewery : CO2
Tunnel: CO
Leak gas detection: CO2, CH6

Thank you very much for
your attention.

Analyser S

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WELCOME TO ANALYSER

Yokogawa India Limited

Date: 11 July 2006

YOKOGAWA INDIA LIMITED

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The water flowing through the piping and components

Typical pH Analysis points :-

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Typical Conductivity Analysis points :-

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Typical DO Analysis points :-

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Yokogawa India Limited

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pH = Activity of Hydrogen ions which defines the

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Membrane made from special glass formulation

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This provides return path for electrical circuit.

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Reference Electrode Glass Electrode

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Process pressure + spring

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ORP / Liquid earth

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Using standard pipe fittings in PVC from your local

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GLC – Ground Loop Current

Increase in impedance due to

Breakage / crack in the sensor

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Traditional pH meters are

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60-80% of measuring problems is caused by plugged,

The impedance of the junction is THE indicator for junction

Glass electrodes are sensitive for breakage. A broken

The impedance of the Glass indicates integrity of the

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In many applications sensors need regular cleaning

Chemical cleaning is most effective way to remove

Good dynamic response guarantees clean and good pH

Dynamic sensor check gives feedback on cleaning

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Automatic wash cleaner

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Contact can be chosen to operate

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EXA series New Millenium

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How often ? once per month !