TDLS200 Tunable Diode Laser Gas Analyzer and its Application to Industrial Process

TDLS200 Tunable Diode Laser Gas Analyzer and its Application to Industrial Process
Kazuto Tamura *1 Yukihiko Takamatsu *1 Tomoaki Nanko *2 Junichi Matsuo *3
Yokogawas TDLS200 laser gas analyzer, which is based on tunable diode laser spectroscopy, features high selectivity and long-term stability, and offers fast in-situ analysis of even high-temperature or corrosive gases. This report introduces the measurement principle of the TDLS200 and an example of real-time residual ammonia measurement in a flue to control ammonia injection volume during the denitration and dust collection process.

INTRODUCTION

laser gas analyzer employing the tunable diode laser absorption spectroscopy (TDLAS) method has a feature capable of measuring the concentration of the sample gas with high selectivity for gas components and without contact only by irradiating the gas sample with light from a tunable diode laser. Thus fast and accurate in-situ measurements can be performed in process lines under various measurement conditions. For example, measurements can be performed at normal temperature and up to temperatures as high as 1500 C, and in environments with fluctuating pressure. It can also measure corrosive or highly hazardous gases. Use of the accurate and highly responsive measurement signals produced by the analyzer for process control systems helps improve yields, energy efficiency, and safety in various industrial processes. A simple configuration without moving parts and components with limited lifespan ensures virtually maintenance-free operation and management. Yokogawas TDLS200 laser gas analyzer is a new type of laser gas analyzer evolved for process measurement. Applying a measurement method based on the peak area integration method, it eliminates errors caused by the presence of other gases and pressure changes, which lead to measurement errors. It also enables accurate measurement of the concentration of gas components, even under simultaneous f luctuations in temperature and other factors. This paper provides an overview of the TDLS200 laser gas analyzer and describes its features and measurement principle, and introduces examples of its applications.

INSTALLATION AND CONFIGURATION OF TDLS200 LASER GAS ANALYZER Fi gur e 1 shows a n ex a m ple of i n s t a l lat ion a nd conf iguration of the TDLS200 laser gas analyzer. The TDLS200 has a launch unit and a detection unit that are usually placed in a facing orientation on either side of the duct (cross duct) through which process gas flows. The cross-duct installation shown in Figure 1 can accommodate ducts up to approximately 20 m wide.
Semiconductor laser Launch unit (Light emitter) Optical path length Measuring laser beam Mounting flange (on both sides) Process gas flow Optical axis alignment (on both sides) Photodetector (Photo diode) Detection unit (Light receiver)

Purge gas for preventing contamination of the optical window (on both sides)

Figure 1 Installation and Configuration Example of the TDLS200 Laser Gas Analyzer Optical windows separate the interior of the analyzer from the process gas. The light from the semiconductor laser in the launch unit goes through the optical window, the process gas and the optical window of the detection unit and reaches the photodetector. The photodetector converts the power of the received laser beam into an electrical signal. The arithmetic circuit in the launch unit determines the absorption spectrum of the measured component, calculates the peak area of the spectrum, converts it into component concentration, and outputs it as a 4 to 20 mA analog signal. The optical axis alignment part has a bellows structure that allows easy angle adjust ment while maint ai ni ng airtightness essential for the industrial process. The connection of the launch unit and the detection unit via the optical axis alignment part enables easy optical axis adjustment not only for regular installation configuration where the

*1 Analytical Products Business Center, Industrial Automation Business Headquarters *2 Quality Assurance Dept., Industrial Automation Business Headquarters *3 Laser Analysis Division, Yokogawa Corporation of America

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TDLS200 Tunable Diode Laser Gas Analyzer and its Application to Industrial Process two units are placed on both sides of the pipe as shown in Figure 1, but also for various types of installation like those shown in Figure 2. This makes it possible to determine the installation configuration that best suits the components to be measured and the application to ensure optimal conditions for measurements.
Minimum optical path length 36 inches 24 to 14 inch 24-inch pipe concentric reducer Minimum optical path length 36 inches

0.0025

Absorbance [A.U.]

0.002 0.0015 0.001 0.0005 0 1.528

1.53

1.532

1.534

1.536

1.538

Wavelength [m]
Minimum optical path length 36 inches

Figure 4 CO2 Absorption Spectrum Component Selectivity of Tunable Diode Laser Spectroscopy Figure 5 shows the absorption spectra for CO 2 and H 2O. A wavelength resolution of conventional spectrometers for the infrared to near-infrared region is around 0.3 to 3 nm. This value is equivalent to or larger than the distance between absorption peaks of different gases (0.5 nm or less), making it impossible to resolve gas absorption peaks. This example explains the case measuring concentration of CO2 in the presence of H 2O. A conventional spectrometer will be affected by H 2O spectrum interference. To reduce the effect of interference, measures such as removing interfering gases must be taken prior to measurement.
The distance between CO2 and H2O peaks is 0.5 nm or less and cannot be resolved by conventional spectrometers
0.005 0.0045 0.004 0.0035 0.003 0.0025 0.002 0.0015 0.001 0.0005

36-inch pipe 36 to 14 inch concentric reducer Minimum optical path length 36 inches

Restriction

Figure 2 TDLS200 Installation Configurations MEASUREMENT PRINCIPLE OF THE TDLS200 LASER GAS ANALYZER The TDLS200 uses the TDLAS method to measure optical absorption spectra peculiar to molecules ranging from infrared to near-infrared due to vibration and rotation energy transition of molecules in the measured component through a semiconductor laser with an extremely narrow spectral linewidth. The optical absorption spectra peculiar to major molecules such as O2, NH3, H2O, CO and CO2 are in the region from infrared to near-infrared, and measurements of the amount of light absorbed (absorbance) at a specific wavelength make it possible to calculate the concentration of the measured component. Infrared and Near-infrared Absorption Spectra Due to Molecule Vibration and Rotation Figure 3 shows an example of molecule vibration and rotation mode (1) while Figure 4 shows a typical CO 2 absorption spectrum in the infrared to the near-infrared range. Molecules consisting of two or more atoms absorb light at frequencies specific to the vibration and rotation modes of stretching, scissoring, etc. as shown in Figure 3. The width of absorption band for CO 2 shown in Figure 4 is about 10 nm and the spectral linewidth of each absorption peak is approximately 0.05 nm.

Absorbance [A.U.]

CO2 CO2 H 2O

1.533

1.5335

1.534 1.5345 Wavelength [m]

1.535

1.5355

Figure 5 CO2 and H2O Absorption Spectra In contrast, unlike low resolution spectrometers, the TDLS200 uses a laser beam with an extremely narrow spectral linewidth emitted by the tunable diode laser, and its wavelength can be changed by adjusting laser temperature and drive current. This makes it possible to measure a single absorption peak among those in the absorption spectrum like that shown in Figure 5. Thus, as shown in Figure 6, one absorption peak that is not affected by interfering gases can be selected for measurement. Since wavelength selectivity is high and measurements are not affected by other interfering components, there is no need to remove interfering gases prior to measurement, allowing in-situ measurement of process gas.

Symmetric stretching

Antisymmetric stretching

In-plane scissoring

In-plane rocking

Out-of-plane wagging

Out-of-plane twisting

Figure 3 Examples of Molecule Vibration and Rotation Modes

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TDLS200 Tunable Diode Laser Gas Analyzer and its Application to Industrial Process
CO2 absorption peaks not subject to interference with other gases
0.005 0.0045 0.004 0.0035 0.003 0.0025 0.002 0.0015 0.001 0.0005

Absorbance [A.U.]

CO2 CO2 H 2O

1.533
0.002 0.0018 Absorbance [A.U.] 0.0016 0.0014 0.0012 0.001 0.0008 0.0006 0.0004 0.0002 0 10 20

1.5335

1.534 1.5345 1.535 Wavelength [m]

1.5355

Select only single CO2 peak not subject to interference with other gases

wavelength scanning signal. However, all of these methods were greatly affected by changes in temperature, pressure and coexisting gases. In contrast, the peak area integration method is theoretically not affected by changes in coexisting gas components and spectrum area remains constant. And the spectrum area changes linearly with pressure changes in principle. As shown in Table 1, the effect of temperature, pressure and coexisting gas components on the peak height method and the 2f method are nonlinear, which makes compensation difficult when more than one of these factors are involved. Since the peak area integration method per mits linear compensation for gas pressure changes and non-linear compensation for gas temperature changes, it ensures accurate compensation.
0.014

30

40

50

60

70

80

90

100 110 120 130 140 150

Data no.

Absorbance [A.U.]

Figure 6 Absorption Spectrum Measured Using TDLS200 Measurements of Component Concentration Using Peak Area Integration Method The TDLS200 is capable of measuring an accurate spectrum without being affected by interfering components by sweeping the oscillation wavelength of the semiconductor laser around a single absorption peak of the component to be measured. Although an absor ption spectr um obtained by the TDLS200 isolates it from interfering components, the shape of the spectrum varies depending on the broadening effect caused by the following factors: gas temperature, gas pressure, coexisting gas components. Therefore measurements subject to such environmental changes require compensation. Figure 7 shows the changes of a 0.76 m-band single absorption spectrum of O2 with a 10% O2 concentration caused by temperature changes, pressure changes and inclusion of CO2, N2 or He as background gases respectively. The TDLS200 sweeps a wavelength using a semiconductor laser and measure absorption spectra, and calculate component concentration from the spectrum area employing the peak area integration method. Table 1 shows a comparison of the influence of each factor on the peak area integration, peak height and 2f methods (2). Table 1 Factors Affecting Spectra and Comparison of their Effects
Factors causing changes Gas temperature Gas pressure Coexisting gas components Peak area integration Peak height method / method 2f method Nonlinear Nonlinear Linear Nonlinear No effect Nonlinear

0.012 0.01 0.008 0.006 0.004 0.002 0 50 100 150 200 250

296 K 396 K 496 K

(a) Absorption spectrum when temperature changes

0.014

Data no.

300

Absorbance [A.U.]

0.012 0.01 0.008 0.006 0.004 0.002 0 50 100 150 200 250

0.5 atm 1 atm 1.5 atm

300

(b) Absorption spectrum when pressure changes

0.014 0.012

Data no.

Absorbance [A.U.]

0.01 0.008 0.006 0.004 0.002 0

1 8

10% O2 in CO2 10% O2 in N2 10% O2 in He

15 22 29 36 43 50 57 64 71 78 85 92 99 106 113 120 127 134 141 148

(c) Absorption spectrum when other gas is mixed

Data no.

Figure 7 Changes in Absorption Spectra Caused by Temperature, Pressure, and Coexisting Gasses EXAMPLES OF INDUSTRIAL APPLICATIONS MEASUREMENTS OF RESIDUAL NH3 CONCENTRATION IN FLUE GAS The TDLS200, thanks to its capability of fast in-situ measurement in actual processes, can be applied to high-speed control where signals indicating component concentration measurements essential for management are directly delivered to process control systems, and can be applied to real-time management of process states as well. The TDLS200 can thus

Conventional methods used so far include the peak height method that calculates the concentration of measured components from the peak height of absorption spectra, and the 2f method that calculates the concentration of the measured component from the P-P (Peak to Peak) value of the waveform generated by the frequency doubling modulation from a 53

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TDLS200 Tunable Diode Laser Gas Analyzer and its Application to Industrial Process help improve various industrial processes. In this section, we will introduce measurements of residual NH3 concentration in flue gas. Note that optimum combustion control applications have been reported in another Yokogawa technical report (3). Please refer to that report for details. Ammonia (NH3) gas is injected into flue gas to remove NOx (denitration), increase the efficiency of a dust collector and prevent corrosion. Excess NH3 injection increases the running costs and the amount of residual NH3, resulting in generation of foul odors. Therefore, the amount of NH3 in the exhaust gas must be measured, controlled and monitored. For example, the exhaust gas denitration equipment for a large combustion furnace uses the DeNOx SCR (selective catalytic reduction) process, where NOx is reduced to N2 and H2O by NH3 injection and selective reduction catalysis, and residual NH3 concentration (ppm level) in the flue gasses is measured online. Conventional NH3 meters that use indirect NOx measuring methods such as the chemiluminescence detection and ion electrode method have slow response and require sample line equipment involving heated pipes to prevent NH 3 adhesion and large maintenance costs depending on such a complex measurement system. On the other hand, as shown in Figure 8, the TDLS200 is installed directly into process lines and measures NH 3 , which substantially improves responsiveness and maintainability. In addition, the highly responsive NH3 concentration signals can be employed in NH3 injection control to optimize NH3 injection.
FIC
NOx

Figure 10 shows the changes in NH3 injection volume and measurement values of TDSL200 in the case where denitration equipment for improving the efficiency of the dust collector and preventing corrosion is not equipped with; TDSL200 is installed at point A in Figure 9.
Volume of injected ammonia [kg/h] Volume of injected ammonia [kg/h]
16 12 Volume of injected ammonia 14 12 10 8 6 TDLS indicated value 4 11:00 11:30 12:00 12:30 13:00 13:30 14:00 14:30 0 15:00 10 8 6 4 2

TDLS indicated value [ppm]

Time
12 10 Volume of injected ammonia 10 8 6 4 2 0 12:00 12:30 13:00 13:30 14:00 14:30 15:00 15:30 8 6 4 2 TDLS indicated value 13:14 Boiler stoppage 14:32 Boiler restart 0 -2 16:00

TDLS indicated value [ppm]

Time

Figure 10 NH3 Injection Volume and Changes in Measured Values of TDLS200 CONCLUSION This paper has presented an overview of the TDLS200 laser gas analyzer and described its features, measurement principle, and applications. The high component selectivity, fast response and ease of maintenance achieved by this technology and product assure its application in a broad range of industrial processes. These include not only use in the NH3 measurement applications introduced in this paper, but also in measurements of CO and O2 in optimum combustion control, measurements of minute amounts of water in electrolytic plants, etc. We expect the TDSL200 to greatly contribute to the preservation of the environment and reduction of running costs through its applications to process control not limited to monitoring. REFERENCES

Control of NH3 injection volume

NH3 injection Denitration equipment DeNOx SCR TDLS200

High-speed measurement of residual NH3

Figure 8 Use of TDLS200 in Denitration Equipment for Measurement and Injection Control of NH3 Figure 9 shows an installation location examples of the TDLS200 in an exhaust gas denitration process of a boiler.

Examples of TDLS200 installation location

Economizer Denitration equipment

Point of NH3 injection Point of NH3 injection (When denitration equipment is not provided)

A B

Air heater

Dust collector

(1) The Chemical Society of Japan compiled by, The Fifth Series of Experimental Chemistry Vol. 9 Spectroscopy and Diffraction I, Maruzen Co. Ltd., 2005 in Japanese (2) Masayuki Satou, New type of laser gas analyzer technology and its application to industrial processes, Instrumentation Control Engineering, Vol. 52, No. 2, 2009, pp. 73-76 in Japanese (3) Yoshitaka Yuki, Akihiro Murata, Optimum Combustion Control by TDLS200 Tunable Diode Laser Gas Analyzer, Yokogawa Technical Report English Edition, Vol. 53, No. 1, 2010, pp. 19-22 * TDLS is a trademark of Yokogawa Electric Corporation.

Figure 9 Installation location examples of TDLS200 in exhaust gas denitration process of a boiler

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