TYPES OF PROCESS ANALYZERS

An analyzer is an instrument or device which

conducts chemical analysis (or similar) on
samples or sample streams

• Analyzers – auto-analyzers
• Allows a sample stream to flow from the
process equipment into an analyzer,
sometimes conditioning the sample stream in
between such as reducing pressure or
changing the sample temperature.
 Destructive and Non-destructive
Analysis
Destructive Analysis: sample stream is modified by the
analyzer
• e.g. reducing the pressure, changing the sample temperature, addition of
reagents
• Sample stream cannot be returned to the process

Non-destructive Analysis: sample stream is not substantially

modified by the analyzer
• relies upon use of electromagnetic radiation, sound, and inherent
properties of materials to examine samples
• sample stream can be returned to the process
 Online vs. Inline Analysis

Online analysis: analyzer is connected to a

process, and conducts automatic sampling

Inline analysis: a sensor can be placed in a

process vessel or stream of flowing material to
conduct the analysis
 TUNABLE DIODE LAZER ANALYZERS
SPECTROSCOPY (TDLAS)
• a technique for measuring the concentration of
certain species such as methane, water vapor and
many more, in a gaseous mixture using
tunable diode lasers and laser absorption
spectrometry
• Can achieve very low detection limits (of the
order of ppb)
• also possible to determine the temperature,
pressure, velocity and mass flux of the gas under
observation
• Group IV-VI semiconductor material lasers
• Operate in 3 – 30 um spectral range
• A basic TDLAS setup consists of:
– tunable diode laser light source,
– transmitting (i.e. beam shaping) optics,
– optically accessible absorbing medium,
– receiving optics and
– detector/s
 OXYGEN ANALYZERS
(Lambda Analyzers)

• an electronic device that measures the

proportion of oxygen (O2) in the gas or liquid
being analyzed
• Zirconia oxygen analyzer (ordinarily operate at
a high temperature close to 800°C)
• Paramagnetic oxygen analyzer
 Principle
(Zirconia Oxygen Analyzers)
Determines oxygen concentration using the conductivity of a
zirconia ceramic cell. Zirconia ceramic cells only allow oxygen
ions to pass through at high temperatures.

• Reference gas on one side and sample

gas on the other side
• Oxygen ions move from the side with the
highest concentration of oxygen to that
with the lowest concentration.
• The movement of ions generates an EMF
(Electro Motive Force) which can be
measured to determine the oxygen
content.
 the EMF varies
depending on • the zirconia sensor is
placed in a constant
• the temperature of the
temperature oven
zirconia sensor and
• the oxygen concentration • air is generally used as
of the reference gas (PR), the reference gas
in the actual device.
 Limitations
• Flammable gases cannot be used
• Sensor degradation occurs if corrosive gas
(fluorine-based gases, chlorine-based gases,
sulfate-based gases)is measured
• In general, these analyzers cannot be used
with closed loops (circulating systems) unless
they are specially designed for that purpose.
The sensor may be damaged by excess
pressure.
 Paramagnetic Oxygen Analyzers

High magnetic susceptibility of oxygen

as compared to other gases allows it to
be attracted to a magnetic field

Magnetic susceptibility is a measure of the

intensity of the magnetization of a substance
when it is placed in a magnetic field
Focused magnetic field is
created

Nitrogen filled glass spheres are

mounted on a rotating suspension
within the field

Mirror mounted on the

suspension – detects the
displacement of the nitrogen
spheres as oxygen is attracted to
the strongest part of the field

Reflected light is directed on to a pair

of photocells – light intensity
converted to electrical signal - which
is fed to a feedback coil causing a
motor effect to keep the suspensions
in place
 Limitations

The difference in magnetic susceptibility

between the dumbbell and the gas
sample is very subtle for low oxygen
concentrations, this method is used only
when measuring percent levels of oxygen
and not for trace levels
 INFRA-RED GAS ANALYZER

Measures trace gases by determining the

absorption of an emitted infrared light source
through a certain air sample

• Gas detector doesn't directly interact with the gas

• Gas molecules only interact with a light beam

• Non-destructive analysis
 Methods used for Detection

Rise in temperature of Photon detectors

gas molecules (Absorption Spectrum)
Molecules resonate at
Molecules of a specific gas
frequencies of radiation
absorb radiations of
matching with their natural
specific wavelengths
frequencies

Increase in vibrations cause Transmitted spectrum

an increase in temperature indicates the absorbed
of the gas wavelengths
 Structure and Operation

When a "detector"
The infrared light is
chamber absorbs some
emitted and passes
of the infrared The combination of
through the sample
radiation, it heats up output voltages from
gas, a reference gas
and expands. This the detector chambers
with a known mixture
causes a rise from the sample gas
of the gases in
in pressure within the can then be compared
question and then
sealed vessel that can to the output voltages
through the "detector"
be detected either with from the reference
chambers containing
a chamber.
the pure forms of the
pressure transducer or
gases in question.
with a similar device.
 DUST MONITORING SYSTEMS
Two basic methods of dust emission reporting

Mass concentration
Mass flow (kg/hr)
(mg/cubic meter)

Total mass of dust

Most commonly used
emitted per unit time

Assumes a
Absolute measure of
homogeneous mixture
dust emission
of dust particles and air
 Mass concentration
Measurement of mass concentration depends factors that
change the volumetric characteristics of the carrier gas:

• Gas law effects: the effects of temperature and pressure.

• Dilution effects: the effects of excess air and water vapor levels.

Data normalization is required

• standard practice is to report the data as a mass per normal cubic meter
of dry gas, at a specified level of oxygen.
 Drawbacks
• A simple measurement becomes a complex
measurement
• Cost of measuring the gas normalization
parameters is greater than the cost of the
primary dust measurement
– Schedule A processes: normalization data is
already available as part of the gas analysis
requirements
– Schedule B processes: which are only required to
measure dust, the problem becomes severe
 Mass Flow
The measurement is related to mass concentration.

• Mass flow = mass concentration x volumetric flow

No normalization data is required

• Does not depend in any way on gas temperature, pressure, oxygen or water
vapor values, or on any form of dilution of the exhaust gases.

Mass flow can be directly related to the environmental impact

 Operating Principle
(Grimm Aerosol DMS#365)

Single particle count – using light

scattering technology

Semiconductor laser as light source

Mirror reflects the scattered light beam to be

detected by a photodiode

Pulse height classifier classifies photodiode

signals in a multichannel size classifier

Counts are displayed and stored

 GAS CHROMATOGRAPHY
• used to separate organic compounds that are volatile
• consists of:
– a flowing mobile phase,
– an injection port,
– a separation column containing the stationary phase,
– a detector, and
– a data recording system.
 Principle
The organic compounds are separated due to differences
in their partitioning behavior between the mobile gas
phase and the stationary phase in the column.
 Oven
Injection
port
He

Detector

Recorder-
computer
Carrier Gas
Column

Sample vaporizes and Components of the The separated

is forced into the sample mixture interact components pass
Sample is injected column by the carrier with the stationary through a detector.
phase so that different Electronic signals,
(using a syringe) into gas ( = mobile phase substances take collected over time, are
the injection port. which in GC is usually different amounts of sent to the GC software,
helium or any other time to elute from the and a chromatogram is
inert gas) column generated.
 Temperature Dependence of
Partitioning Behavior
the separation
Partitioning column is
behavior is usually
dependent on contained in a
temperature thermostat-
controlled
oven

Process is similar to fractional distillation

A gas chromatography oven

Separating components with a wide range of boiling points is

accomplished by starting at a low oven temperature and increasing
the temperature over time to elute the high-boiling point
components
 GC Detectors

• Separated components of the mixture must

be detected as they exit the GC column

• Thermal-conduc. (TCD) and flame ionization

(FID) detectors - two most common detectors
on commercial GCs.
 Thermal Conductivity Detector (TCD)

Senses the changes in the thermal conductivity of

the column effluent with reference to a flow of
carrier gas

• Also known as Katharometer

• Bulk property detector and chemical specific
detector
• Non-specific and non-destructive
• Universal detector – responds to all compounds
TCD – an electrically heated filament in a
temperature controlled cell
• During elution of an analyte, thermal conductivity of
the column effluent reduces
• Filament heats up and changes resistance
 Limitations

• Less sensitive than other detectors

• Has a larger dead volume
• Cannot operate below 150 C temperature set
• Chemically active compounds may damage
the filament
 Flame Ionization Detector (FID)
• Measures the concentration of organic species
in a gas stream
• Most sensitive gas chromatographic detector
• Has a low detection limit in the picogram or
femtogram range
• Has a linear range of 6 to 7 orders of
magnitude
 Operating Principle

Ions formed during the combustion of organic

effluents in hydrogen flame is detected.

• Ion generation is directly proportional to the

concentration of organic species in the sample stream
• Presence of heteroatoms decreases the detector’s
response
 Detector Construction

small volume chamber

gas chromatograph column capillary is directly

plumbed to the bottom of flame jet

column effluents are mixed with hydrogen and

air to be burned up in the flame jet

An electronic igniter (electrically heated

filament) lights on the flame

Charged particles created during combustion

create a current b/w the detector’s electrodes
 Operation

positive electrode doubles as the nozzle head

where the flame is produced

negative electrode is positioned above the flame

(tubular electrode called collector plate)

ions attracted to collector, hit the plate and

induce current

current is measured with a high impedance

picoammeter and fed to an integrator

The response of the detector is determined by the number of

carbon ions hitting the detector per unit time. Thus, the
detector is sensitive to mass rather than concentration.
 Advantages

• Relatively inexpensive to acquire and operate

• Low maintenance requirements apart from
cleaning and replacing of the FID jet
• Rugged construction
• Extensive linear and detection range
 Limitations
• Cannot differentiate between organic compounds
• Cannot detect non-organic substances
• Presence of heteroatoms and oxygenates lower
the response factor
• Carbon monoxide and carbon dioxide cannot be
detected without a methanizer (bed of Ni catalyst
used to reduce CO and CO2 to methane)
• Destructive analysis – all components passing
through the flame are oxidized
 pH ANALYZERS
• pH is a measure of the acidity or alkalinity of
water
• pH is defined as the negative logarithm of
hydrogen ion activity (aH+) in water

pH = -log10 aH+

• In practice, negative log of hydrogen ion

concentration [H+] is used
 Electrode Chain pH Analyzer
Electrodes immersed in a solution form a galvanic cell due to
potential developed on both electrodes, which changes in
response to any change in pH of the solution

• Two electrode setup –

indicator electrode and
reference electrode
• Measures the potential
between reference electrode
dipped in a solution of known
pH and the indicator electrode
Electrode Construction
 pH Meter

Measures the
potential difference
between the
electrodes and
converts it to a
display of pH
 Buffer Solutions and Calibration
• Calibration is done using solutions which
– Have a precisely known pH value
– Are relatively insensitive to contamination from acidic and
alkaline species (i.e. buffer solutions)
• Two different buffers are used for calibration which indicate
electrode sensitivity
 CONDUCTIVITY ANALYZERS
• Conductivity of a solution depends on:
– concentration of ions
– mobility of ions
– valence no. of ions
– temperature
• Two types of conductivity measurements:
– contacting
– inductive
 Contacting Conductivity
• Two metal electrodes in contact
with the solution are used
• Alternating current is applied at
optimal frequency to the
electrodes and output voltage is
measured

Conductivity = Cell constant x Conductance of the Solution

Cell constant – ratio of distance b/w electrodes to area of the electrodes

Conductance of solution – input current / output voltage
 Factors Influencing Measurement
• Polarization and Contamination
of Electrode Surface –
accumulation of ionic species near the
surface and chemical reaction on the
surface
• Field Effects – any interference with
the field lines causes an error in signal
measurement
 Inductive Measurement
• Toroidal or electrode-less conductivity measure
• Two wire wound metal toroids enclosed on a
corrosion resistant plastic body
• Ideal for measuring solutions having high
conductivity
• Can tolerate high levels of fouling by suspended
solids
• Does not come into contact with the electrolyte
 An ionic current The ionic current
A voltage is Electronic
Analyzer applies flows induces an
induced in the current is
an AC voltage to proportional to electronic
surrounding measured by the
the drive coil the conductance current in the
liquid analyzer
of the liquid receiver coil
 Temperature and Conductivity
• Increasing the temperature of an electrolyte
solution increases the conductivity
• 1.5% to 5% increase per degree C
• Conductivity readings are commonly corrected
at a reference temperature, commonly 25 C
• Correction algorithms need to be applied
– Linear temperature coefficient
– high purity water or dilute sodium chloride
– high conductivity or dilute HCl
 Linear Temperature Coefficient

Conductivity of an electrolyte changes by about the

same percentage for every degree rise in temperature

C25 – conductivity at 25 C
Ct – conductivity at T C
- linear temperature coefficient
 High Purity Water (dilute NaCl)
Correction
• Assumes that the sample is
pure water contaminated
with NaCl
• Measured conductivity is
the sum of conductivity of
pure water and the
conductivity from Na+ and
Cl- ions

Conductivity of
conductivity of Add conductivity
pure water at ‘t’
Point 1 – raw Na+ and Cl- at ‘t’ of pure water at
– raw
conductivity at is converted to 25 deg. C -
conductivity =
temp. ‘t’ degree conductivity at corrected
conductivity of
C 25 deg. C (point conductivity
Na+ and Cl- at ‘t’
3) (point 4)
(point 2)
 Cation Conductivity (dilute HCl)
Correction
• Used in steam electric power industry
• Assumes the sample is pure water
contaminated with HCl
• Contribution of water to the overall
conductivity depends on the total amount of
acid present