Process Analysers

000.270.CSE-163.1

Introduction to Process Analysers

Copyright 2007 Fluor Corporation

Discussion Points

1.

What is an Analyser and what makes it a Process Analyser? Why do we need this? Overview of some common Analyser types and how they work Positives & Negatives

2. 3.

4.

5.
6.

Sample Conditioning
Analyser Shelters and Cabinets

What is an Analyser?

Most of the Instrumentation discussed elsewhere deals with the physical attributes of the process (e.g. temperature, pressure and flow) or of the well-being of the plant itself (e.g. vibration, current and valve position). To understand Analysers we need to define

Analysis .. The determination of how much of a given component is in a sample

This is achieved by again using the physical attributes of these components in instrumentation that allows them to be measured and quantified .. this is an Analyser

What make a Process Analyser?

This is usually an automated Analyser complete with safe and effective sample collection, conditioning and disposal
The results produced by the Process Analyser may be required to automatically change the configuration of or even shutdown the process plant. Therefore critical aspects affecting Analyser choice will be: Sensitivity of the Analyser and accuracy of the result

H2S (safety issue) is often measured in the range 0 10 ppm

transport time through a 30m sample line is typically 30 - 60 seconds from continuous monitoring to a new result every few minutes (varies according to project specification) a 24 ball valve may take every few minutes to fully close (varies according to project specification)

Time taken to present the sample to the Analyser Time taken to analyse and report the result Time taken to react to the result

Availability of the Analyser

when an Analyser is calibrating itself it is not reporting new results

Why do we need an Analyser?

Almost all products are produced and sold against a specification which will usually include a minimum purity and maximum allowable amounts of impurities. Any material not meeting this specification cannot be sold and will incur additional costs for storage and reprocessing (or disposal).
An Analyser can often allow the detection of out-of-specification (OOS) processing at an early stage. Early intervention will minimise the quantity of OOS produced. Early intervention can also prevent the OOS material from contaminating an even greater quantity of inspecification material.

Many processes in the chemical. Biochemical, nuclear, Oil & Gas and power industries can produce or use materials that can cause OOS product or which can be independently released and cause harm to people or the environment. Often small process changes can enhance the formation of these materials.
An Analyser can often detect the formation of unwanted materials at source again allowing early intervention (examples of the detection of sulphur impurities in the Oil & Gas industry will be shown)

Analyser Types UV/Vis Spectroscopy

1.4

Continuous monitoring of a sample stream passing through a glass cell using ultraviolet (usually) or visible light. The Analyser measures the difference in intensity between light before and after it has passed through the sample
Different types of chemical structure will absorb light at specific frequencies. Analysis at these frequencies allows us to measure and quantify materials with a specific chemical structure

1.2 1
Absorbance (AU)

0.8 0.6 0.4 0.2

1% SO2 + 1% H2S

1% SO2
240 260

0 220

1% H2S300 280

320

Wavelength (nm )

Example: mixture of Sulphur Dioxide and Hydrogen Sulphide in Air. Immediate action may be needed to increase introduction of air to reduce the H2S component

UV/Vis Spectroscopy (2)

Ametek 900 UV Spectrophotometer
2 x UV lamps plus filter wheel allows measurement at multiple wavelengths. Note long light path for greater accuracy. The calculation is carried out within the analyser and the result (in ppm) is available as 4 - 20 mA or Modbus

1. Analysis at 285 nm allows quantification of sulphur dioxide (SO2) 2. Analysis at 235 nm and subtraction of the now known SO2 component will allows quantification of hydrogen sulphide (H2S very toxic!)

UV/Vis Spectroscopy (3)

Advantages
Continuous process immediate result reporting Robust process the same components will always absorb at the same frequencies. Linear response at low concentrations Easy maintenance - UV lamp replaced at scheduled intervals & optical bench can be replaced for maintenance off-line Quick calibration this is a function of the immediate reporting of results. The time taken is however long it takes to pass the calibration sample into the cell and then remove it again, Complicated optics are temperature and humidity dependent Sample impurities can coat the light cell affecting the measurement Glass components cannot take pressure changes Process impurities will often have a similar absorbance spectrum to the products. An unexpected impurity may not be detected Wide range of responses for different components (in the example almost any instrument could be used to quantify SO2 but H2S in a mixture required multiwavelength detection and complex calculations (if only H2S had been present a simpler instrument could have been used)

Disadvantages

Analyser Types Gas Chromatograph

The sample is injected into a constant flow of carrier gas (usually hydrogen). As it passes along the heated quartz glass column which has been coated with a high boiling gum different components of the sample repeatedly dissolve in the gum and are then re-vaporised at different rates. This process separates components which are each measured in a detector as they emerge from the column Sample injection uses micro flow-switching valves and is controlled by the Analyser. The most common form of detector uses flame ionisation the carrier gas is burnt in air and a potential applied across the flame. As components emerge from the column this electrical current changes and these changes are measured and amplified

Gas Chromatograph (2)

The area of each peak is proportional to the quantity of that component present although the response of each peak may differ. Note this separation took 5 minutes to complete. If there were any higher boiling components present these would interfere with the next sample unless the analytical sequence cleared them from the column

Separation of C4 to C6 hydrocarbons by GC

Gas Chromatograph (3)

Very accurate determination this peak is for 10.15 ppm H2S.
Note this separation took 3 minutes to complete. A much quicker response would be needed if this was a safety system

Analysis of H2S in a waste water stream

N2 gas is bubbled through the waste water sample in the Sample Conditioning Cabinet and the extracted gas injected into the GC

Gas Chromatograph (4)

Siemens Maxum GC

H2S in waste water (see previous slide)

Gas Chromatograph (5)

Advantages
Very sensitive process the method can work at very low component concentration (< 1 ppm) Wide range of detectors, columns and sampling techniques to suit most applications Easy maintenance very little to go wrong (only moving parts are the oven fan and sample injection) and robust components Process impurities can be separately detected and quantified Batch-wise process result reporting after the event (5 to 10 minutes later). Not good for plant control or safety systems where a quick response is required. The quality of the separation is totally temperature dependent. Generally the column oven ensure this is the case. However for accurate or complicated determinations a constant temperature environment is needed. Sample impurities can block the column affecting or even completely stopping the detection. Late running peaks need to be removed before next injection. Long calibration time a calibration run takes the same time a sample as the whole point is to replicate a normal injection but with a known component concentration. For multiple components it may be necessary to calibrate against separate calibration samples, Live flame in the detector requires good separation when used in non-flammable environments

Disadvantages

Analyser Types Paramagnetic O2 Analyser

The paramagnetic oxygen sensor consists of a cylindrical shaped container inside of which is placed a small glass dumbbell. The dumbbell is filled with an inert gas such as nitrogen and suspended on a taut platinum wire within a non-uniform magnetic field. The dumbbell is designed to move freely as it is suspended from the wire. When a sample gas containing oxygen is processed through the sensor, the oxygen molecules are attracted to the stronger of the two magnetic fields. This causes a displacement of the dumbbell which results in the dumbbell rotating.
An opposing current is applied to restore the dumbbell to its normal position. The current required to maintain the dumbbell in its normal state is directly proportional to the partial pressure of oxygen and is represented electronically in percent oxygen.

Paramagnetic O2 Analyser (2)

Advantages
Continuous process with fast response time. Ideal for process control or safety monitoring. Easy, quick and infrequent calibration uses nitrogen (0%) and ambient air (21%) Very specific - impurities (even corrosive components) do not affect detection as the paramagnetic effect is peculiar to oxygen and a few oxygen containing materials

Disadvantages Poor sensitivity (measurement range is from 1 to 100%). Not recommended for trace oxygen measurements Very sensitive to vibration or other detector movement

Analyser Types Infra-red (IR or FTIR) Analyser

Instrument similar to UV absorption. An Infrared (IR) Analyser measure changes in light absorption at a particular IR wavelength as it is affected by the sample. Note it is more complicated than UV absorption in that IR light is absorbed and then re-emitted at different wavelengths as the molecular structure is first excited and then relaxes back to its original energy level.

The signals are relatively weak and noisy. Fourier Transform (FT-IR) is an electronic technique to manipulate and enhance this signal.

Infrared Analyser (2)

Advantages

Continuous process with fast response time. Ideal for process control or safety monitoring. Very specific can be used for components that are very similar in structure or are too inert to have an effect by other techniques

Disadvantages

Poor sensitivity without FT High noise to signal ratio Very sensitive to vibration or other detector movement

Example - Paramagnetic and IR Analysers

ABB Magnos O2 and Uras IR detectors in Analyser Cabinet

Analysis of O2 and SO2 in flue gas (high water vapour content)

Analyser Types Total Organic Carbon

Acid is added to the aqueous sample to convert inorganic carbon to CO2 which is sparged out of the system with an inert gas. The remaining organic carbon is then oxidised to CO2 (various methods) and this is detected and quantified

Organic carbon occurs in municipal water supplies and comes from both decaying organic matter and from organic impurities (such as pesticides) that are eluted into the source water Normally specified to maximum allowable levels in high purity water systems (pharmaceutical / biotechnology / nuclear industries) as well as being monitored in drinking water Used as a test to continuously monitor pharmaceutical cleaning method

Analysers not normally requiring a Shelter

Humidity
Gaseous systems only Detector measures change in conductivity across an absorbent polymer between electrodes In-situ continuously monitoring in-line meter and used for process control or alarm monitoring Aqueous systems only Both can be in-situ continuously monitoring in-line meters Both are normally used for process control or alarm monitoring Both are susceptible to interference by entrained impurities pH meters have thin membranes often on glass and need near-ambient pressure pH meters will transfer tiny amounts of brine into the test solution GCs are now available in EEx enclosures and can be used in hazardous zones Thermal conductivity detection not as sensitive as flame ionisation but allows use of non-flammable gases Currently only available for simple separations

Conductivity and pH

Gas Chromatography (new)

Sample Probe

The probe must be designed to sample near the middle of the pipe away from areas of turbulent flow or where particles might be picked up (probe in left hand diagram is too long)

If removal of the probe is required (either by specification or design) a double block/bleed arrangement may be needed.
In some cases the sample is returned back to the process at the sample point. Some form of sample pump would be needed within the loop. Where sample probes and lines are required to be heated this would usually be controlled from I/O at the analyser

Sample Conditioning
Reasons for Sample Conditioning

Small volume Many analysers require a very small sample (e.g. 1 l typical for GC) Fast loops will be required Residues High boiling components will take a long time to clear GC column Tars will block columns and coat optics Even water will block sample lines and fog optics if it condenses at the wrong time. Initial separation Condensation prior to analysis Change of phase (e.g. extraction of component from an aqueous stream to either a gas or organic solvent prior to GC) Chemical changes to the sample to allow better quantification.

Sample Conditioning
Example SCS Cabinet HGCE Project
Sample stream is waste water containing a demulsifier with potential to contain up to 10 ppm H2S contamination. GC was selected as analyser and extraction of H2S from solution into gas prevents the demusifier interfering with the analysis. N2 is sparged through the sample and this extracted vapour passed to the GC analyser Other operations being carried out are: N2 flow rate control Sample flow rate control with excess bypassing via fast loop SCS cabinet heated to constant 50C Valve time controlled from Analyser to switch between sample and calibration gas

The Shelter - Analyser Environment

The provision and design of an Analytical Shelter will depend on the requirements of the Analyser instrument. This in turn will generate a number of issues for which the criticality and priority will need to be assessed and mitigated.

Changes in the elution time of GC peaks can mean wrong identification and/or changed peak size, More frequent calibration would be required which equates to the analyser being off-line. Therefore constant temperature preferred. Most analyses are greatly effected by temperature and humidity (e.g. precision optics in spectrophotometers). Again constant temperature preferred. Length of sample line? This should be minimised. However there may be a playoff between line length and ideal shelter positioning. Is there a suitable pressure drop to drive the sample to the Analyser? Vendor will need to supply transport calculations Will the automatic calibration span gases be easily available onsite.

Shelter Environment

Does the sample line require trace heating (e.g. to prevent condensation)? Are power and/or instrument air required to drive the sample probe? If so are they controlled from the shelter? Disposal of waste sample and Analyser effluent. Can it go back into the process line (preferred)? Is there a back pressure on the disposal line that could damage the Analyser optics (e.g. a flare header may often have a 3 bar backpressure)? Assume worst case design criteria. Consider the routing of utility pipework, power cables, signal cables, drains and HVAC air intake. These may have to come considerable distances from suitable safe areas via underground trenches or overhead trays and supports

Shelter Safety

Zoning issues. Interior of Shelter may be different from the outside environment. Where is the safest place for the fresh air intake? Safe disposal of toxic and/or flammable process and calibration streams. Safe handling of flammable carrier gases using flow restrictors. Vendor to provide calculations to show maximum possible concentration of toxic and flammable material can never exceed specified limits (not above the TLV (TWA) or 20% of the Lower Explosive Limit see Project and Fluor design criteria) Isolation of Flame Ionisation Detectors. Where the Analyser or other electrical certification does not meet the shelter zone requirement additional certified isolation such as differential pressure enclosures may be required Safe area for instrument engineer attention for maintenance and calibration of the Analysers. Safe and easy access for changing of gas cylinders and maintenance of Sample Conditioning Systems There will be a requirement for a number of safety sensors both in the Shelter and air intake (e.g. smoke detector, flammable, toxic and asphyxiant gases, shelter differential pressure). A Cause & Effect chart should cover each safety eventuality and define the outputs to local and site alarm systems.

Analyser Shelters

Exterior layout detail for Analyser Shelter on Habshan Gas Expansion Project in Abu Dhabi. This shelter contains 4 Ametek UV Spectrophotometers used for H2S determination in various plant locations. HVAC units are to the right hand side

Analyser Shelters

Interior layout drawing of same Analyser Shelter. The entries for the heated sample lines to each of the 4 Analysers can be seen to the left of each instrument on the drawing

Introduction to Process Analysers

Any Questions ?