ANALYTICAL INSTRUMENTS

WHY ANALYSERS ?

PROCESS CONTROL & MONITORING

- QUALITY
- OPTIMISATION

SAFETY
- PERSONNEL
- PLANT
- ENVIRONMENTAL

ANALYTICAL INSTRUMENTS
Analytical instruments should ideally be:
Reliable.
Capable of fast analysis.
Self-calibrating
Able to withstand harsh environments.
Able to tolerate different kinds of samples.
Nondestructive so that the sample can be
returned to the process as it was.
Automated and capable of unattended
operation.

ANALYTICAL INSTRUMENTS
Consistent product quality
Improved process efficiency
Reduced equipment maintenance
Plant and employee safety
Compliance with environmental
standards

ANALYTICAL INSTRUMENTS
Major Industries where analyzers
are used:
Power Generation
Water and Wastewater
Chemical
Pulp and Paper
Refining
Pharmaceutical and Biotech
Industrial Heating
Semiconductor
Food and Dairy

ANALYTICAL INSTRUMENTS
Process monitors that measure and transmit
information about chemical composition, physical
properties, or chemical properties are known as
process analyzer . They are primarily used as
continuous on-line analyzers.
A process monitoring system usually requires a sample
conditioning system, a process analyzer, and one or
more data output devices.
Process analyzers measure chemical concentrations or
physical or chemical properties that can be used as
control variables instead of relying on indirect physical
parameters, such as pressure, temperature, and
inferred data from computer models.

Analyzer Selection Design

Requirements
A)

ECONOMIC CONSIDERATIONS
Analyzer systems can
improve product quality
increase product throughput and output
reduce energy costs.

Analyzer Selection Design

Requirements
B) ENVIRONMENTAL AND SAFETY
CONSIDERATIONS
Analyzers are used to detect
Hazardous plant conditions
For monitoring government-mandated
requirements concerning pollutants in
ambient air, stack emissions, and effluent
streams.

Analyzer Selection Design

Requirements
C) APPLICATION REQUIREMENTS
How the analyzer system will be used
Quality control
Process control
Safety/environmental regulations

ENVIRONMENTAL AND SAFETY

CONSIDERATIONS
Continuous Emission Monitoring
Systems

Continuous emission monitors (CEM)

commonly measure concentrations
of pollutants prior to their release to
the environment.

ENVIRONMENTAL AND SAFETY

CONSIDERATIONS
Non-dispersive Infrared Analyzers (NDIR)
NDIR analyzers consist of an infrared light source,
a sample cell and a detector system.
Chromatography or non dispersive infrared
techniques
to
analyze
for
carbon
monoxide(CO), a product of incomplete
combustion.
Gas chromatographs are used to measure such
pollutants as vinyl chloride, hydrogen sulfide,
benzene,
ammonia,
and
other
sulfur,
chlorinated, and hydrocarbon compounds.

ENVIRONMENTAL AND SAFETY

CONSIDERATIONS
The following gases can be measured by
NDIR analyzers
sulfur dioxide (SO2),
oxides of nitrogen (NO and NO2),
carbon monoxide (CO)
carbon dioxide (CO2).

CHEMICAL PROPERTY
ANALYZERS
pH ANALYSERS
CONDUCTIVITY ANALYSERS
DISSOLVED OXYGEN ANALYSER

CHEMICAL PROPERTY
ANALYZERS
Common liquid electrochemical
measurements include
hydrogen ion concentration (pH),
oxidation-reduction potential,
electrolytic conductivity
Ionization is the basis for the measurement
of pH, electrolytic conductivity, and
oxidation-reduction potential (ORP).

CHEMICAL PROPERTY
ANALYZERS

Typical Applications:
Wastewater and Pure Water Treatment
pH Measurement in Food & Dairy Industries
Corrosion Detection
Dearator Efficiency
Aeration, Effluent, Stream and Aquaculture
Monitoring
Industrial Drying
Heat Treating Furnaces and Gas Generators
Natural Gas Pipelines
Turbine Monitoring
Sterilization

CHEMICAL PROPERTY
ANALYZERS
Typical refinery applications for pH
measurement include:
a. Refinery wastewater.
b. Cooling tower water.
c. Boiler feed water.
d. Crude tower overhead systems.
e. Corrosion control in processing facilities.

pH Analyzer
pH is a measure of the hydrogen ion (H+)
concentration in an aqueous solution. It is
used widely as a measure of the degree of
acidity or alkalinity of a solution.
The electrode measuring system is
comprised of three elements: the glass
measuring electrode, the reference
electrode, and the sensing element for
automatic temperature compensation.

pH Analyzer
the pH value is determined by measuring
the voltage potential developed between
the process stream and the standard
solution contained within the glass
measuring electrode. This potential is
developed because of the difference in
hydrogen ion concentration of the two
solutions.
The reference electrode is designed to
produce a constant potential regardless of
the solution in which it is immersed.

pH Analyzer
There are two types of reference electrodes
diffusion
flowing.
In the diffusion-type reference electrode, the
electrolyte diffuses through a large porous
area to contact the process.
In flowing-type electrodes, a small amount of
the electrolyte constantly flows out of the
reference electrode creating a conductive
path between the electrode and the process
stream.

pH Analyzer
Temperature compensation
Due to the fact that the electromotive
force developed by the glass electrode will
be affected by the temperature of the
electrode itself, a temperature
compensator is usually necessary. The
compensator consists of a resistance
thermometer built into the probe, which is
immersed in the process stream.

pH Analyzer

Oxidation-Reduction Potential
(ORP)
Ionized solutions contain particles that convey
electrons. The development of an oxidationreduction potential involves the transfer of
electrons in a solution.
When a voltage is applied to electrodes
immersed in the solution, ions in the solution
migrate. In this cell, the positive particle (M+)
approaches the cathode and picks up an
electron, reducing its positive charge. This is
called reduction. At the anode, the negative
particle (X) loses an electron to the anode and
becomes more positive. This is called oxidation.
These reactions are called oxidation-reduction
or redox reactions.

Electolytic Conductivity
Measurement
Electrolytic conductivity is the ability of a
solution to conduct electric current. It is
referred to as specific conductance or simply
conductivity. Specific conductance is defined
as the mho (siemen), which is the reciprocal of
the resistance in ohms of 1 cubic centimeter
of the liquid at a specified temperature.
The common unit of measurement in
conductivity is the micromho (microsiemen),
which is one millionth of a mho (siemen).

Electolytic Conductivity
Measurement
The electrical conductivity of a wastewater
stream, usually measured in microsiemens per
centimeter (mS/cm), is a measure of the
dissolved ionized salts in the stream The
conductivity of distilled water may be as low as
1 mS/cm, and that of sea water as high as 50
mS/cm.
An increase in wastewater conductivity indicates
an increase in ionized substances in the stream,
which could be caused by strong acids or bases
and indicates that specific analysis is required.

Electolytic Conductivity
Measurement
CONDUCTIVITY CELLS
The conductivity cell typically consists of two metal
plates or other electrodes firmly spaced within an
insulating chamber that serves to isolate a portion
of the liquid.
Cell Constants
The conductance between two electrodes varies as
follows:
C A/L
where.
C = conductance, in mhos (siemens),
A = area of electrodes, in square centimeters,
L = distance between electrodes, in centimeters.

Electolytic Conductivity
Measurement
Conductivity Sensors
Conductivity measurements are widely
used in industry. Most applications involve
water treatment and range from
desalination to the production of high
purity water in the power and
semiconductor business. Other
applications include detecting leaks in the
heat exchangers and sensing liquid
interfaces

DISSOLVED OXYGEN IN WASTEWATER

ANALYSIS
The quantity of dissolved oxygen in a
wastewater stream, usually measured in
parts-per-million, is a measure of the
streams ability to support aquatic life.
Typical analysis spans: 0 20 ppb up to 0
20 ppm
Typical analyzer outputs: 0 1VDC, local
meter,
4 20mA

TYPES OF OXYGEN
ANALYZERS
There are two basic types of oxygen
analyzers currently suitable for refinery
process stream applications:
electrochemical principle
paramagnetic principle.
Other methods of oxygen analysis include
gas chromatography, oxygen/combustibles
analyzers, and dissolved oxygen
analyzers.

OXYGEN ANALYZERS
Oxygen analyzers may be used to ensure
that sufficient oxygen to support life is
available.
Process conditions frequently require the
use of an inert gas to purge or blanket
vessels. Oxygen may be a contaminant
that would cause degradation of the
contents of the vessel or enable an
explosive mixture to exist.

Electrochemical Oxygen
Analyzers
Electrochemical oxygen analyzers consist
of at least two metallic electrodes in good
electrical contact with an appropriate
electrolyte. The chemical reactions
occurring in the cell produce an output
current or voltage, which is a function of
the number of oxygen molecules diffusing
into the interface between the electrolyte
and the measuring electrode

Electrochemical Oxygen
Analyzers
The various types of electrochemical
analyzer cells are conveniently classified
by the type of electrolyte used:
a. Aqueous solutions of various metal salts
and soluble organic compounds.
b. Zirconia ceramic doped with
combinations of calcia, yttria, and scandia.

Electrochemical Oxygen
Analyzers
Oxygen molecules diffuse through the
membrane to the cathode. At the cathode,
they are reduced to OH ions upon
acceptance of four electrons produced by
an appropriate reaction at the anode. The
reactions occur in a cell comprised of a
platinum cathode, silver anode, and
potassium chloride electrolyte.

Electrochemical Oxygen
Analyzers
The materials used in these cells depend
upon manufacturers designs and may be
operated in a variety of modes at
temperatures between 32F and 122F
(0C and 50C)
The output of the cell in the amperometric
mode of operation is a current proportional
to the number of oxygen molecules
reaching and being reduced at the
cathode/electrolyte Interface.

PARAMAGNETIC OXYGEN
ANALYZER

PARAMAGNETIC OXYGEN
ANALYZER

PARAMAGNETIC OXYGEN
ANALYZER

Electrochemical Oxygen
Analyzers
Zirconia electrochemical type: High temperature
zirconia electrochemical cells consist of a thin section
of doped zirconia, usually a disk or a tube, whose
opposite surfaces are coated with porous platinum
electrodes. When operated at a temperature of about
1562F (850C), the voltage difference between the
two electrodes is proportional to the log of the ratio of
the partial pressures of oxygen existing at the two
electrode/electrolyte interface.
Instrument quality dry air is normally used as the
reference gas on one side of the cell, while the other
side is exposed to the sample gas.

Electrochemical Oxygen
Analyzers
These high temperature probes do not
have heaters, but a temperature sensor is
provided, and the analyzer output is
temperature corrected.
Any combustible gases present in the
sample or reference gases will be burned
completely before the gases reach the
surface of the electrodes because 1562F
(850C) is well above the ignition
temperature of fuel gases.

Heated Probe-type Zirconia Electrochemical Oxygen

Analyzer Schematic Diagram

ZIRCONIA OXYGEN ANALYZER

ZIRCONIA OXYGEN ANALYZER

Electrochemical Oxygen
Analyzers
Available Ranges and Limits of Various
Methods

a. Electrochemical cells:
1. Fuel cells, 0 2 ppm to 100% O2.
2. Polarographic, 0 5 ppm to 100% O2.
3. Coulometric, 0 1 ppm to 100% O2.
b. Paramagnetic analyzers: 0 1% to 0 25%.
c. Zirconium oxide: 0 2.5% to 0 25% (21%
maximum output).

Electrochemical Oxygen
Analyzers
The zirconium oxide method is generally
limited to flue gas analysis. The main
advantage is that the sample system is
reduced to a minimum.

Gas Chromatography
Sulfur content, which remains appreciable
through the refining process, is generally
an unacceptable contaminant and must be
reduced or eliminated from the end
product.
To minimize pollution, most industrialized
countries have adopted laws prohibiting
the burning of fuels containing high sulfur
concentrations.

Gas Chromatography
Most sulfur analyzers in common use
today use the electromagnetic energy
absorption characteristics of the various
chemical forms of sulfur.
Instruments used for sulfur content
analysis include the gas chromatograph,
the mass spectrometer the thermal
conductivity

Gas Chromatography
The accurate analysis of sulfur compounds
in the gaseous state is commonly done
with gas chromatography.
The sulfur components most often
monitored in stack emissions are SO2 and
H2

Gas Chromatography
Gas chromatography is a flexible method for
analyzing several components in a gas
discharge stream. For example, a gas
chromatograph with a Flame Photometric
Detector (FPD) can be used to analyze
sulfur compounds such as H2S and SO2.

Gas Chromatography
The gas chromatograph is used to obtain online composition information of selected
process streams for current process
operation.
The gas chromatograph may be designed to
determine concentration of one or more
components in a multi-component stream.
This type of chromatograph can determine
component concentrations from parts-perbillion (PPB) ranges 100%.

Non-dispersive infrared absorbance system(NDIR)

Non-dispersive infrared absorbance

system(NDIR)

GENERAL CONCEPTS
GENERAL CONCEPTS ON
SAMPLE HANDLING SYSTEMS
CALIBRATION GASES/ LIQUIDS
ANALYSER HOUSES

SAMPLE HANDLING SYSTEM

Sample handling system of a process analyser is
a device or combination of devices which
transfers a sample from a process stream to the
analyser in such a way as to minimise
maintenance and to preserve or enhance the
analytical information contained in the sample.

IDEAL SAMPLE HANDLING

SYSTEM
Contains no moving parts
Contains no components which requires
cleaning /servicing
No transportation lag
Preserve /enhance the analytical
information contained in the sample.

SAMPLE HANDLING
SYSTEM
SAMPLE TAKE-OFF POINT.
SAMPLE TRANSPORT SYSTEM.
SAMPLE CONDITIONING SYSTEM.
SAMPLE RETURN AND/OR
DISPOSAL SYSTEM

SAMPLE TRANSPORT
SYSTEMS
A SINGLE LINE TO THE
ANALYSER
Vent / Drain
A

Used only if

THE SAMPLE LINE VOLUME IS SMALL COMPARED TO THE ANALYSER

SAMPLE CONSUMPTION.

THE ANALYSERS ARE INSTALLED CLOSE TO THE SAMPLE TAKE-OFF

POINT IN THE FIELD.

e.g. Conductivity or pH Analyser.

SAMPLE TRANSPORT
SYSTEMS

A SINGLE LINE WITH BYPASS STREAM

Vent / Drain / Sample Recovery System

A
Vent / Drain / Sample Recovery System

* This ensures a very high Velocity in the sample line. Hence a

reduced Transportation lag.
* This system is applicable when no return point is found for a Fast
Loop.
* The Bypass stream is connected to a vent or a drain or a sample
recovery unit.

RESPONSE TIME
Analyser response function contains a pure lag time
& the time constant .
Lag is the time Delay between Input & the
appearance of output.

Lag is due to Transmission lines

Lag time TL = Volume in m3/volume flow rate
(m2/sec) = Line length / velocity

SAMPLE CONDITIONING
FILTRATION
Single line to the analyser
The filter shall be located at the sample
take-off point itself.
Used to remove particulate which causes
interference (choking).
All analysers should be fitted with a strainer
near the sample take-off point so that the
downstream components are protected from
damage & blockage due to larger particles.

SAMPLE CONDITIONING
When sampling hot wet stack gas, a filter capable
of withstanding the gas temperature
is installed
at the beginning of the sample line to prevent
solids from entering the gas sample line.
After the sample is cooled the sample goes to
coalescing filter to remove suspended liquids.
Cool the sample below ambient at the upstream of
the coalscer to aid condensation & to heat the
sample line gently at the downstream.

SAMPLE CONDITIONING
Pressure regulators:Delivers sample at
constant pressure & volume flow rate to the
low pressure side , ie Analyser .
Why Pressure regulators ?
1.

Analyser not rated for Process Pressure

which is very high - Reduce pressure
2. Analyser requires flow at constant pressure
for accurate analysis - Maintain pressure

SAMPLE CONDITIONING
TEMPERATURE CONTROL
Temperature control is effected by coolers & heaters
Temperature must be maintained above a dew point so that a
representative sample is obtained at the analyser.
The sample lines must be traced.
Sample composition can be affected if the lines are heated or
cooled excessively.

Gaseous samples containing condensables/ liquid samples

will require the line to be heated up to prevent condensation in
the first case & to prevent precipitation or freezing in case of
the latter

SAMPLE DISPOSAL

RETURNING THE LINE TO THE PROCESS .

Ensures no hazard to

RELEASING TO ATMOSPHERE

Clean, non-flammable , non-toxic

Environment
Analyser
Process

* Gas samples can be vented to the atmosphere.

* Liquids to the chemical drain.

Corrosive or toxic gases

* Scrubbed before disposal.

Flammable gases
* Vented to flare stack .
* Diluted to a safe level

SAMPLE DISPOSAL

VENTS
There are only seven flammable gases,
which are lighter than air.

Hydrogen
Methane
Ammonia
Acetylene
Hydrochloric acid
Ethylene
Carbon monoxide

All other flammable gases and all other flammable

vapours are heavier than air. They can flow across the
ground covering wide areas.

CALIBRATION

CALIBRATION GASES / LIQUIDS

Calibration gases: shall be stored in
mounted horizontally mounted cylinders
which can be shaken .
Calibration liquids:
* When mixtures of liquids are stored in
cylinders these should only be partially filled.
The rest of the portion shall be filled with
an inert gas such as N2 at such a pressure
as to not let the liquid vaporise and then
fractionate.

CALIBRATION
* Calibration fluids - Zero fluid & Span fluid
* Zero Fluid : used for checking the Analyser Zero
* Zero fluid contains none of the component of interest ,
but has quality which correspond to the Analyser
* E.g. Nitrogen of suitable purity is often used as the zero
gas.
* Span / calibration Fluid : Used for checking the analyser
span. It is an accurately made-up mixture containing only
the components to be measured ,but may contain an
inert diluent. Span fluid should have a quality
corresponds to 70% of the analyser reading.

MOUNTING OF ANALYSERS
* Field mounting of Analysers
Field mounting of analysers may only be considered
when:
The cost of an analyser house would
disproportionate to the anticipated advantages

be

The selected location of the analyser house(s) would

result in unacceptable time lags.
The sample is non-flammable and the proposed
mounting position is in a safe area.

MOUNTING OF ANALYSERS
Field mounted - 2 pipe mounting , wall
mounting types

Cabinet mounted

Analyser house

Analyser shelter

MOUNTING OF ANALYSERS
Weather protection
Field mounted analysers shall be provided with adequate
protection against;
Rain

Sun radiation

Process and water spills

In some cases, shielding against radiant heat from

surrounding equipment must be provided.

ANALYSER HOUSE (AH)

THE OBJECTIVES :

Create a non-hazardous atmosphere

So that testing or calibration and maintenance of
the analyser can be performed with casings
opened and electrical circuits alive.

Create a good environment

In which analysers and their associated
equipment are adequately protected against
adverse whether conditions.

ANALYSER HOUSE (AH)

SAFETY :
External explosion hazards
Internal explosion hazards
Flammable Gases / Vapours

Flammable Liquids

ANALYSER HOUSE (AH)

* The Analyser House should preferably be a
separate building.
* When the ventilation system is in the
operation of Under the specified conditions &
the purging (if required ) has been completed
, the atmosphere inside the
AH shall be non-hazardous in spite of the
external area classification.

ANALYSER HOUSE (AH)

* It is also necessary to take into account of the
characteristics of non- explosion protected
apparatus,which may affect the safety of Analyser
Houses on ventilation failure.
* False ceiling/flooring shall be avoided.
* Cable trenches shall be avoided.
* All the pipes/tubes supplying flammable substances to
the Analyser house should be capable of being
isolated outside the Analyser House.

ANALYSER HOUSE (AH)

Quantity of flammable material in the
Analyser house to be kept minimum for the
normal operation of the equipment installed.
Provide efficient ventilation system to dilute
the level of flammable gas or vapour in case
of an internal release.
Provide safe disposal of samples.
* All electrical equipment intended to remain in
operation during ventilation failure shall have
protection suitable for Zone 1.

ANALYSER HOUSE (AH)

Lighting and emergency Tele phone shall confirm to

Zone 2 requirement.
Switch off power to non-explosion protected instruments
on ventilation failure.
Use gas detectors to detect leakage & Power shall be
switched off on reaching 20 % of LEL.
The sample conditioning equipment shall be mounted on
the outside wall close to the location of the relevant
analyser and be adequately weather protected
Isolate the lines handling hazardous material to the
Analyser House.

END