New Developments in Continuous Emission Monitoring Systems (CEMS)

Bill Worthington, ABB Inc. Analytical Products

The Clean Air Act was passed in 1969 in an attempt to clean up the air in the United States. Though considered progressive at the time, the Clean Air Act of 1969 has proven insufficient and was thus amended in 1990 with sweeping revisions in an attempt to curb the three major threats to the nations environment and to the health of millions of Americans. These three threats are acid rain, urban air pollution, and toxic air emissions.

The acid rain program of the Clean Air Act Amendments of 1990 (CAAA) has fostered the growth of Continuous Emissions Monitoring Systems (CEMS) by requiring more than 250 coal burning power plants to install CEMS during Phase I of the CAAA and another additional 2000 plants to install CEMS in Phase II. Phase I was effective on January 1, 1995 and Phase II becomes effective on January 1, 2000. These CEMS are in addition to the already existing CEMS that were required by the earlier New Source Performance Standards (NSPS) and other existing regulations. These regulatory

pressures have promoted the growth of the CEMS and continuous analyzer from its infancy to its now current mature state. During this period of time, the analytical

equipment has progressed from analog instruments born in the laboratory to new digital analytical equipment designed for the specific applications.

CEMS can broadly be broken into 3 types of methods:

Extractive, In-situ, and

Parameter. The extractive methods can be further broken into two techniques, direct source level and dilution. In-situ methods can be either path or point types. Parameter methods rely on physical measurements such as temperature, pressure, or other process measurements to predict emissions and are thus do not incorporate on-line analytical techniques.

In the acid rain program, the dilution extractive techniques have predominated due to

the desirability of a wet basis measurement.

These types of systems have been

successful to this point, but have severe limitations as pollutant concentrations reach continually lower levels. Variables such as stack temperature, stack pressure, and molecular weight have an unfavorable impact on the dilution technique. A dilution

sample system is not appropriate where an analyzer with the requisite sensitivity is not available. In general, reactive and condensable gases such as HCl, NH , and formaldehyde
3

present the greatest measurement challenges.

Such gases may react with other

components within the stack gas stream; they may condense or be absorbed by liquid condensate within a cold extractive sampling system, they may adsorb onto surfaces, or they may polymerize before reaching the analyzer. Thus, depending upon the

components making up the flue gas stream, special sampling equipment may be needed and special operation and maintenance procedures may be required to achieve reliable results.

Both extractive methods rely on similar analytical techniques. A summary of current techniques includes nondispersive infrared gas analyzers, ultraviolet gas analyzers, chemiluminescent gas analyzers, paramagnetic oxygen, flame ionization detection gas analyzers, gas chromatography, mass spectrometry, and Fourier transform infrared analyzers.

A brief overview of these analytical techniques and advances in their technologies follows.

Nondispersive infrared gas analyzers (NDIR) utilize several different detection techniques. Opto-pneumatic detectors, commonly known as Luft detectors (from their inventor, Karl Luft), interference filter photometers (IFC), and gas filter correlation (GFC) are the more predominant types. The theory of operation of these infrared methods is similar and is based upon absorption of infrared energy in the 2 to 11 micron wavelength range. Simple molecules with less than 5 or 6 atoms have infrared

absorption spectra with fine structure. Gases fitting this description are ideal for Luft and GFC types of analyzers, which correlate the spectra of the sample gas with the spectra of the pure component of interest. Interference filter correlation is capable of measuring gases with either fine structure in the spectra or broadband absorption.

Recent developments in NDIR analyzers include the ability to have multiple optical benches in one analyzer and stacked detectors that result in as many as four (4) gases being measured in a single instrument. Microprocessors have added many capabilities to modern NDIR analyzers which include a platform approach such as utilized by ABB, Hartmann & Braun, where a single system controller provides the user interface for as many as 3 analytical modules. The system controller provides industry wide interfaces to control systems and common computer networks. MODBUS is included for control systems and Ethernet is provided for interfacing to personal computers. The interference filter correlation (IFC) photometric analyzers such as the ABB Multiwave have been enhanced through microprocessor technology to measure multiple components and also operate over analyzer networks. These analyzers have also

been successfully applied to hot wet measurement demands by heating to temperatures as high as 200 C.

Improvements have also been made in the calibration of NDIR gas analyzers. By using calibration cells, small optical cells with actual test gases encapsulated within, analyzer calibration can be checked without bottles of expensive test gases.

Ultraviolet (UV) analyzers are in general more sensitive than NDIR analyzers. Another advantage of UV analyzers is that water (H2O) is transparent to UV. SO2 and NOx are frequently measured with this technology. Other possibilities are NO2, H2S, CS2, COS, Cl2, NH3, and other gases. The state of the art UV analyzer utilizes a 4 beam optical approach so that a double quotient can be formed and removes variables such as dirty windows and aging of components so that the result is a more robust and stable analyzer.

Paramagnetic analyzers are commonly used to measure oxygen.

Paramagnetic

analyzers are normally used in CEMS to measure oxygen as the diluent gas. Newer analyzers of this type are more resistant to corrosion and are smaller than their predecessors, which results in a faster more stable response. There are several types of paramagnetic analyzers. The more widespread is the dumbbell type or more

properly, magnetodynamic, which uses a small dumbbell shaped optical component to physically determine the oxygen concentration. These have the limitation of having moving parts and optical components exposed to the sample gas, which may be corrosive. Another type of paramagnetic is the Magnetic wind or thermomagnetic type of analyzer, where there are no moving parts and the construction is of highly corrosion resistant materials, which results in an extremely robust analyzer with a long service life. Microprocessor technology has also advanced paramagnetic analyzers by allowing for surrogate calibration mixtures for difficult or impossible to prepare gas mixtures or very toxic mixtures.

Chemiluminescence is a technique that has been used to measure NO. Widely used for CEMS with low NOx levels, chemiluminescent analyzers provide good sensitivity and selectivity to NO.

Flame ionization detection (FID) techniques are widely used to measure hydrocarbons. During the combustion of organic substances, in a hydrogen flame, electrically charged particles are produced. The resulting current of these ions is proportional to the organic carbon content. FIDs have very large dynamic ranges, from 10 to 100,000 mg of organic carbon / cubic meter. The state of the art hydrocarbon analyzer utilizes a heated system from the point of the sample interface throughout the entire analytical system to avoid cold spots where heavier hydrocarbons may adsorb and cause erroneous results. sample pumps. Eductor systems eliminate the troublesome problem of heated Modern FID analyzers feature self-monitoring, automatic fault

recognition and logging functions. Some FID analyzers, such as the ABB Hartmann & Braun Multi FID also include options for a sparger, or water stripper to measure volatile organics in water.

Gas Chromatography is a very versatile analytical technique that separates the sample stream into its individual components for measurement. The process ,or on-line gas chromatograph differs dramatically from its laboratory counterpart, the only common area being the separation concepts. In current practice, designs integrate a basic

analyzer (chromatograph) and controller & microprocessor package. These systems can perform as stand alone units or be interfaced with multiple chromatographs, distributed control systems, or a host computer. Significant changes have been made in valves, columns, column systems and detectors. Tough polyamide coated fused silica columns with stabilized stationary phases have reached a high level of reliability and are routinely used in Process Chromatographs. The most popular detectors for online chromatographs are still the thermal conductivity and flame ionization detectors, but other component selective detectors are being used including electron capture, flame photometry, photoionization, and chemiluminescence. Process chromatographs are used in CEMS when the pollutant of interest is more exotic than the criteria pollutants. The CAAA lists 188 hazardous air pollutants, most of which can be reliably measured by online chromatography.

Mass spectrometers have been a basic laboratory tool for many years. The mass spectra of a compound provides a positive fingerprint identification of that compound. Mass spectrometers also have inherently broad chemical applicability because the ionization process is fairly uniform for all compounds. One instrument can measure many compounds providing a cost effective means of monitoring. They are inherently fast, sensitive, and capable of wide dynamic range (parts per billion to 100%). The Mass Spectrometer is quantitative and linear since its output is directly proportional to the concentration of the species in the sample. It is a reliable, stable and low

maintenance instrument because it is electronically based rather than chemically based as are many single sensors. Finally, the mass spectrometer has maximum flexibility because its broad capabilities can be selectively used under programmable microprocessor control.

Recent advances in technology have been made which provide the elements necessary for continuous online applications such as CEMS and air monitoring. These

developments include: The turbo molecular vacuum pump, which allows operation in minutes, highly reliable, and low maintenance; The quadrupole filter, which provides measurement of any mass from 0-400 amu; low cost computing power, and packaging for continuous operation environments.

The mass spectrometer is used often to measure hazardous air contaminants which require fast analysis. In situations where many sample points are required, the speed of analysis allows a multistream sampling concept to be used. Eighty (80) port valves are used by ABB Extrel to monitor many sample points through out a plant or process. Thus the flexibility of this instrument makes it possible to monitor many different streams using several different methods for several different gases (up to 40).

Fourier Transform Infrared analyzers are another technology that has been taken from the laboratory and used online for CEMS. microprocessors have made this possible. The advent of inexpensive and powerful One advantage of this method is that

several gases can be monitored at the same time by the same instrument. Heated versions are available that make it possible to monitor hard to handle gases like HCl and NH3 down to 10 ppm. These units find application in the monitoring of combustion sources, toxic waste incinerators, and industrial processes as well as ambient monitoring applications for hazardous air pollutants.

Basically, the FTIR is able to produce a very detailed infrared spectra over a range of typically 2.5 to 25 microns wavelength. Through the power of modern microprocessors, the spectra is calculated from an interference pattern and matched mathematically with the sample data held in memory. A variety of algorithms have been developed to obtain the concentration values from the wealth of data provided by this instrument. An

interesting feature offered by this technique is the storing of digital spectra, not just the calculated values. At some later time, the stored spectra can be processed to

determine concentrations of other gas components that were deemed unimportant at

the time. For example, if a process upset caused the release of gases not normally present, the spectra could be evaluated to determine if the release actually occurred and to what extent.

The operation of the FTIR system is controlled completely by the PC software, enabling the following functions: Display of all measured results and status messages on the monitor, manual interactive operation of the system during commissioning and servicing, remote diagnosis by modem, self diagnosis, and archiving of measured data and self diagnosis data.

The demand created by the environmental regulations of the 1990s together with the advent of economical powerful microprocessors has moved CEMS further along the development curve by focusing on features that save time and money. For example, the Advance Optima concept put forth by ABB Hartmann & Braun uses a common microprocessor platform that standardizes operation of a number of satellite analytical modules. This improves the efficiency of the CEMS and its operating personnel by using a consistent approach to all phases of a project from the planning stages to design, operation, maintenance, training, and spares stocking. The Advance Optima system also makes future system expansion economical and fast.

At the heart of the Advance Optima concept are the analyzer modules: Modules are available for NDIR, Oxygen (paramagnetic and electrochemical), Thermal Conductivity, Flame Ionization, and Ultra violet. This allows a quick configuration from standard modules to build a multi component analyzer for the specific application, whether CEMS or process monitoring.

Industry standard computer interfaces enable easy connection to plant DCS by MODBUS. An Ethernet interface with TCP/IP protocol allows connecting Advance

Optima to PCs or networks. Software modules are available for visualization of the system or remote control. Advance Optima also incorporates PLC like functionality to control and monitor sample system components and report their status over the

standard interfaces. Drivers are also available (Optima ActiveX) for the creation of custom applications under Windows 95/NT in standard programs such as Microsoft Excel, Access, or Visual Basic.

Thus the promise of increased productivity through microprocessor technology is realized in CEMS through extended online time and remote maintenance capabilities. Sometimes the best predictor of the future is the past. History indicates CEMS and other types of environmental monitoring can not only satisfy regulatory requirements but can assist with production cost reduction and efficiency in many cases. Technology and products are available to make most measurements. The formula to the best and most successful monitoring project is to find the most cost effective approach, that has the best workable solution and is in the hands of the end user. Customers, suppliers, and government agencies must work together to achieve realistic and cost effective protection of our environment regardless of the methods chosen.