Calculation of gas concentration Laser gas analyzer. Gas analyzers Laser SITRANS SL. Functionality complex

The invention can be used in the production of electroluminescent devices. The mixture of one-component electroluminophore of the alternating color of the glow base based on zinc sulfide includes the following components, wt.%: Copper single chloride CUCl - 0.05-0.15; Manganese fluoride MNF 2 · 3H 2 o - 0.2-0.45 or manganese nitric acid Mn (NO 3) 2 · 6N 2 O - 0.196-0.43; ammonium halide - 0.5-1.5; Zinc chloride ZnCl 2 · H 2 O - 0.25-1, or zinc bromide ZnBr 2 0.28-1.2; Acid oxalic H 2 C 2 O 4 · 2N 2 O, or hydrazine sulphate N 2 H 4 · H 2 SO 4, or hydroxylamine sulphate (NH 2 OH) 2 · H 2 SO 4, or hydroxylamine Solyasian NH 2 OH · HCl - 1-3; sulfur s - 2-4; Zinc Sulfurous ZNS is the rest. As a halide of ammonium, the mixture may contain ammonium NH 4 Cl chloride, ammonium NH 4 BR bromide or ammonium iodide NH 4 I. The components of the mixture are thoroughly stirred, sieved and calcined in a reducing atmosphere at 850-1050 ° C. The calcined luminophore is cooled, differ and subjected to chemical treatment, dried and sifted. The invention allows to increase the brightness of the electroluminophore, more than 2 times, increase the service life of devices, ensure the change in color at a constant level of brightness. 1 Z.P. F-lies, 1 tab.

The technical field to which the invention relates.

The invention relates to luminescent technique, in particular to the compositions of the mixture to obtain a single-component electroluminophore of the alternating color of the glow based on the zinc sulfide used in the production of electroluminescent devices.

BACKGROUND

The composition of the charge used to obtain sulphide electroluminophores activated by copper, manganese or their mixture obtained by the preparation of a mixture containing zinc sulphide or zinc and cadmium, the corresponding activator and coactivator, calcining it under the coal layer, followed by a water wash with a water solution of potassium oxide hydrate and hydrogen peroxide, while the coactivator is introduced in the charge in the form of zinc or zinc halides and cadmium (see A.S. USSR No. 510497, CL. C09K 1/12, publ. 09.06.1976).

The absence of ammonium halides in the composition;

Lack of reducing agents;

The non-optimal ratio between copper and manganese in the composition of the charge;

A large number of manganese;

Various luminescence colors are achieved at the expense of individual phosphors emitting blue, green, yellow, orange colors separately.

The mixture is known for obtaining an orange color of the zinc sulfide-based glow, including compounds of manganese, copper and sulfur, and it contains carbon dioxide and iodine copper as compounds of manganese and copper at the following ratio of components, weight.%:

(See A.S. USSR №865884, CL. C09K 11/14, publ. 09/25/1981).

The disadvantage of this charge is:

The absence of ammonium and zinc halides (smooth);

Use of one-way copper (activator);

Contains a small amount of reducing agent due to the use of carbon dioxide;

Low luminance brightness.

The closest in technical essence and the achieved positive effect and adopted by the authors for the prototype is the charge for obtaining an alternating color of the glow color based on zinc sulfide, including compounds of copper, manganese and sulfur (Kazankin O.N. and others. Inorganic phosphors, L.: Chemistry , 1975, p.134-135).

The disadvantage of this charge is the impossibility of ensuring the change in the color of the glow from yellow-orange to blue through white, depending on the conditions of electro-excitation at a constant level of brightness of the glow due to the non-optimal ratio between copper and manganese in the charge, a large number of manganese.

Disclosure of the invention.

The task of the present invention is the creation of the composition of the mixture to obtain a single-component electroluminuminophore of the alternating color of the glow of zinc sulfide, which provides a change in the color of the glow from yellow-orange to blue through white, depending on the electro-excitation conditions (see table) at a constant luminance brightness level with color impact and an increase in service life.

The technical result that can be achieved with the help of the present invention is reduced to improving the brightness of electroluminophores, color purity and an increase in service life.

The technical result is achieved with the help of the mixture to obtain a single-component electroluminophore of the alternating color of the zinc sulfide-based color, including compounds of copper, manganese and sulfur, while it additionally contains ammonium halide or zinc, as well as one compound from a row comprising oxalic acid, sulfate hydrazine Hydroxylamine sulfate or salt-crushed, and zinc chloride or bromine zinc is taken as zinc halides, as a compound of copper - a manganese fluorinist or nitric acid, with the next ratio of these components, wt.%:

In the mixture as ammonium halide, it contains ammonium chloride NH 4 Cl, ammonium bromide NH 4 BR or ammonium iodide NH 4 I.

The essence of the preparation of the single-component electroluminophore of the alternating color of the glow is based on zinc sulfide.

The composition of the charge for obtaining a single-component electroluminophore of the variable color of the glow based on zinc sulfide activated by copper and manganese includes the following components (wt.%):

The components of the mixture are thoroughly stirred, sieved and subjected to calcination in a reducing atmosphere at a temperature of 850-1050 ° C. The calcined phosphor is cooled, dispelled and subjected to chemical treatment with traditional electroluminophores in the manner, after which the finished phosphor is dried and sifted.

The introduction of additional components provides the creation of a reducing atmosphere due to their thermal decomposition by reactions, respectively:

The decomposition products of these substances or mixtures thereof displace air from the reaction zone, preventing the phosphor from the oxidation of air oxidation, and also ensure the introduction of the activator - copper - into the crystal grille of the phonophore (zinc sulfide) as the Cu + ions. This leads to an increase in the brightness of the tightness of the electroluminophore in 2 or more times, as well as to an increase in stability in operation, which is unattainable without the use of these components.

Implementation of the invention.

Examples of specific performing the preparation of the mixture for one-component electroluminophore of the alternating color of the glow based on zinc sulfide.

Example 1. To the zinc sulfide sandpaper weighing a mass of 93.5 g, sequentially 0.04 g of copper is added, 0.1 g of manganese fluoride or 0.1 g of manganese nitric acid, 0.2 g of ammonium chloride or 0.2 g of ammonium bromide or 0 , 2 g of ammonium iodide or 0.1 g of zinc chloride or 0.1 g of zinc bromide, 0.5 g of oxalic acid or 0.5 g of sulfate hydrazine or 0.5 g of sulfur hydrazine or 0.5 g of hydroxylamine sulfur, 1 g sulfur.

The mixture is stirred for half an hour and sieved without a residue. The obtained mixture is falling asleep in tigly from carbon-containing material and calcined at a temperature of 800 ° C for 1.5 hours.

The calcined luminophore is cooled to room temperature 18-20 ° C, unloaded from crucible, differ under the UV lamp, with λ max \u003d 365 nm, sieved and subjected to chemical processing as follows:

100 ml of the solution of the following: 100 g of the luminophore is adhering to 100 ml of the following composition:

Add 10 ml of hydrogen peroxide solution (32% solution) and heated to a temperature of 70-80 ° C with constant stirring. Upon reaching the specified temperature, heating is stopped, the mixture is allowed to stand and decanted the solution. The entire cycle spend 15 minutes. For complete washing of phosphor, 5 processing cycles are repeated, after which the phosphor is laundered with water to a neutral reaction by serving 250 ml of water per 100 g of phonogram. Total 5-6 cycles. Washing luminophore is dried in a drying cabinet at T ° 110-120 ° C for a day before dusting.

The resulting phosphor has a very low brightness of the luminescence at electric excitation (1-2 cd / m 2) and unsatisfactory color. Color change comes from yellow to green.

Example 2. To the zinc sulfide sandpaper weighing a mass of 93.5 g, sequentially 0.05 g of copper is single-mero, 0.2 g of manganese fluoride or 0.196 g of manganese nitric acid, 0.5 g of ammonium chloride, or 0.5 g of ammonium bromide, or 0 , 5 g of ammonium iodide, or 0.25 g zinc chloride, or 0.28 g of zinc bromide, 1 g of oxygen acid, or 1 g of hydrazine of the sulk acid, or 1 g of sulfur hydroxylamine, or 1 g of sulfur hydroxylamine, 2 g of sulfur.

Further treatment is similar to the method described in Example 1, the calcination temperature of 900 ° C.

The resulting electrolumino is the brightness of the glow of 12-15 kD / m 2. The color of the glow varies from yellow to blue, including cold-white.

Example 3. To the zinc sulfide sulfide weighing a mass of 93.5 g, 0.15 g of copper is single-mero, 0.45 g of manganese fluoride, or 0.43 g of a nitric acid manganese, 1.5 g of ammonium chloride, or 1.5 g of ammonium bromide, or 1.5 g of ammonium iodide, or 1 g of zinc chloride, or 1.2 g of zinc bromide, 3 g of oxygen acid, or 3 g of sulfate hydrazine, or 3 g of sulfur hydroxylamine, or 3 g of sulfur hydroxylamine, 4 g of sulfur.

Further processing is similar to the method described in Example 1, the calcination temperature of 1050 ° C.

The obtained electroluminum has the brightness of the glow of 13-16 kD / m 2. The color of the glow changes from yellow-orange to violet, including heat-white.

Example 4. To the hint of zinc sulfide weighing 93.5 g, sequentially 0.2 g of copper of a single core, 0.5 g of manganese fluoride, or 0.5 g of manganese nitric acid, 2 g of ammonium chloride, or 2 g of ammonium bromide, or 2 g of ammonium iodide, or 1.5 g of zinc chloride, or 1.6 g of zinc bromide, 4 g of oxalic acid, or 4 g of sulfur hydrazine, or 4 g of sulfate hydroxylamine, or 4 g of sulfur hydroxylamine, 5 g of sulfur.

Further processing is similar to the method described in Example 1, the calcination temperature of 1100 ° C.

The resulting electrolumino is has a low brightness of the glow of 5-6 kD / m 2. The color of the samples is unsatisfactory. Color change occurs in the range from yellow-orange to yellow-green. White color of the glow is unattainable.

Thus, an increase in either a decrease in the ratio of components leads to a deterioration in the electroluminophore indicators, and the obtained electroluminophore according to examples 2 and 3 is optimal and meets all specified indicators.

The dependence of the color of the luminophore samples from the operating exclusion conditions.

The proposed invention compared to the prototype and other well-known technical solutions It has the following advantages.

Characteristic

The device is intended for the operational gas analysis of atmospheric air by the method of optical-acoustic laser spectroscopy

The principle of operation of the gas analyzer is based on the generation of acoustic waves in the air when the modulated laser beam interacts with the gas impurity molecules absorbing laser radiation at a given wavelength. Acoustic waves are converted by microphone into electrical signals proportional to the concentration of absorbing gas. Rebuilding the wavelength of the laser and using known spectral data on the absorption coefficients of various gases, it is possible to determine the composition of the detectable gas impurity.

A distinctive feature of this gas analyzer is to combine in a single design of a rebuilt waveguide CO2 laser and a pumping optical-acoustic detector (OAD) of a differential type. Oda is located inside the laser resonator and forms a single design with a laser. Due to this, the losses on the optical elements are reduced, the power is increased inside the ODAS working channel and the rigidity of the entire structure. The gas analyzer is used automatically rebuilt on the lines a waveguide CO2 laser with a high-frequency (RF) excitation, in which the pulse-periodic generation mode is set by the modulation of the power of the RF generator, which makes it possible to optimize power consumption by adjusting the exhaust pulses of excitation. In the design of the differential type used, there are two resonant acoustic channels, in

which are formed antiphase acoustic waves, which makes it possible to minimize the air flow through the channels with the introduction of appropriate processing.

These features of the device are unique and in combination ensure the sensitivity of detection for optical and acoustic devices, low level Hardware noise and relatively small total energy consumption.

The gas analyzer is able to register the minimum absorption coefficients of gas impurities in the atmosphere in the gas stream at ~ 5 × 10-10 cm - 1 with high speed inherent optical methods Gasanalysis. Thanks to these qualities, as well as the possibility of restructuring the wavelength of laser radiation in the region of 9.3 ÷ 10.9 μm, the gas analyzer allows for real-time measurement of small concentrations of atmospheric and anthropogenic gases (at level 1 PPB and less), such as C2

N4, NH3, O3, C6, SO2, SF6, N2

O, CH3, CH3I TD,

including a pailer of explosive and poisoning substances (only about 100 substances).

These properties make it possible to apply the device to control the concentrations of chemical molecular compounds in atmospheric air and technological processes, carry out an analysis of exhaled air in order to identify various diseases, etc.

Application effect

The obvious advantages of the OA method in combination with the use of sufficiently powerful continuous tunable laser frequency make it particularly attractive to solve problems requiring measurement of weak absorption of radiation with molecular gases. First of all, this concerns the problems of gas analysis at small and ultra-low concentrations of molecules in the medium.

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Highly sensitive laser gas analyzer Designed to analyze the content of impurity gases in air samples. The main elements of the gas analyzer: a waveled CO 2 -Laser, a resonant optical acoustic cell, as well as a computer, in the library of which contains information about the absorption lines of 37 gases. Information about the gas detection limits of the gas analyzer developed by the gas analyzer is presented. The detection limit over ammonia with an error of 15% is 0.015 PPB.

The need for constant control over the content of a large number of pollution in significant areas under reasonable costs of funds and labor is set to equip the environmental control service with gas analyzers that meet the following requirements: 1) the detection threshold at the level of maximum permissible concentrations of analyzed substances; 2) high selectivity in relation to strangers; 3) Analysis multicompanence; 4) high speed (small measurement cycle time during single sample fence), providing the ability to work in motion and relatively fast response to the excess of the specified level of concentration; 5) the continuity of measurements for 2-4 hours to determine the size of the contaminated area.

The existing methods for detecting gases can be divided into traditional (non-specter) and optical (spectroscopic). The work lists the advantages and disadvantages of the main traditional methods in terms of their use for analyzing gas impurities of complex composition in the air.

Spectroscopic methods, the rapid development of which is determined by the unique characteristics of lasers, allow you to eliminate the basic disadvantages of traditional instruments and provide the necessary speed, sensitivity, selectivity and continuity of analysis. In most cases, the average I.K.-region of the spectrum, where the main oscillatory bands of the overwhelming majority of molecules are concentrated to detect air pollution by spectroscopic methods. Visible and U.F.-area in this regard are less informative.

A special place in the family of IK-Laser gas analyzes occupy devices with 2 -Laser-Mi. These lasers are durable, reliable and easy to use and allow you to detect more than 100 gases.

The gas analyzer (sample) is described below, satisfying the above requirements. As a source of radiation, a waveguide CO 2 laser is used, a sensitive element is a resonant optical-acoustic cell (R.O.A.Y.). The optical-acoustic method is based on the registration of a sound wave, excited in a gas when absorbed by the amplitude of laser radiation in R.O.A. The pressure of the sound wave proportional to the specific absorbed power is recorded by the microphone. The structural scheme of the gas analyzer is shown in Fig. 3.1. The modulated radiation from 2 -L-ZER falls on the wavelength restructuring unit. This node is a diffraction grid that allows the rebuilding of the radiation wavelength in the range of 9.22-10.76 microns and receive 84 laser lines. Next, radiation through the system of mirrors is sent to the sensitive volume of R.O.A., where those gases are recorded that absorb the radiation incoming into it. The energy of absorbed radiation increases the gas temperature. Separated on the axis of the cell heat by, mainly, convection is transmitted by the walls of the cell. The modulated radiation causes the corresponding change in the temperature and gas pressure. The change in pressure is perceived by the membrane of the capacitive microphone, which leads to the appearance of a periodic electrical signal, the frequency of which is equal to the radiation modulation frequency.

Figure 3.1. Structural scheme of gas analyzer

Figure 3, 2 presents the sketch of the inner cavity R.O.A.Y. It is formed by three cylindrical active volumes: symmetrically located volumes 1 and 2 with a diameter of 20 mm and internal volume 3 with a diameter of 10 mm. Input 4 and output windows are made of BAF 2 material. The microphone is mounted at the bottom of the cell and is connected to the active volume of the hole 6 with a diameter of 24 mm.

Figure 3.2 Interior cavity of the resonant optical acoustic cell. 1, 2 - external volumes, 3 - internal volume. 4, 5 - inlet and output windows, 6 - microphone hole

The optical resonance "caused by the absorption of laser radiation with gas, under normal conditions occurs at the radiation frequency of 3.4 kHz, and the background signal due to the absorption of radiation by windows R.O.A.Ya., maximum at a frequency of 3.0 kHz. Quality in both cases is\u003e 20 . Such a design R.O.A.I. provides high sensitivity of the gas analyzer and allows you to suppress the contribution of the background signal using a frequency and phase-selective amplifier. At the same time, R.A.Ya. is insensitive to external acoustic noise. Amplitude electrical signal when measuring the concentration is determined by the formula

where k is a permanent cell is the radiation power of the laser, b - the absorption coefficient of gas radiation, C - gas concentration.

A gas analyzer is calibrated before measurements using calibration gas (CO2) with a known concentration.

The measurement of amplitude is carried out using the board of A.P.P., which is part of the computer company Advantech. The same computer is used to control the wavelength rearrangement unit and calculating the concentrations of measured gases.

The developed information processing program is intended for a qualitative and quantitative analysis of the mixture of gases on the absorption spectrum of the laser radiation with 2 laser. The source information for the program is the measured absorption spectrum of the analyzed gas mixture. An example of a nitrogen absorption spectrum, built in units of optical thickness, shown in Rice3,3A, and in Fig. 3.3b is an example of a absorption spectrum with a small addition of ammonia.

Figure 3.3 absorption spectra: A - nitrogen under normal atmospheric pressure, b - mixture of nitrogen ammonia.

Optical thickness where

Cm -1 atm -1 - the absorption coefficient of the j-th gas on the i-oh laser line, with i, atm - the concentration of j-th gas, I

The library of the possible component contains the values \u200b\u200bof the absorption coefficients and is a matrix dimension (n x m). The number of the gases presented in the library T \u003d 37, the maximum number of analyzed laser lines N - 84 (21 lines in each branch of CO 2 -Laser).

In the process of analyzing the spectrum of the gas mixture formed by overlapping absorption lines of those part of the mixture of gases, the program selects from the library those components that allow the best way to describe the mixture spectrum. One of the main search criteria for the best set of the component is the size of the standard deviation between the experimental and found as a result of the iterations by the absorption spectrum:

The algorithm for solving the inverse problem - the search for concentrations according to the known absorption spectrum - was built using the Gauss exclusion method and the regularization method for Tikhonov, and the main difficulties of its implementation are associated with an assessment of the resolution of the solution (elements of the absorption coefficients matrix, as well as free members, are known only approximately ), the choice of the regularization parameter and finding the criteria for the termination of the iterative process.

The table presents the estimated information about the limits for the detection of some gases by the described gas analyzer:

Main operating characteristics of the gas analyzer: the number of simultaneously measured gases - to 6; Measurement time 2 min; The detection limit for carbon dioxide 0.3 RRT: the detection limit over ammonia 0.015 PPB: measurement range by carbon dioxide 1 RRT -10%; Measurement range in ammonia 0.05 PPB-5 RRT; Measurement error 15%; Power supply voltage 220V ± 10%. [ one]

For manuscript rights

Dolgiy Sergei Ivanovich

Laser gas analyzers based on differential absorption method

01.04.01 - Instruments and methods of experimental physics

dissertations for the degree of candidate of physical and mathematical sciences

Barnaul - 2004.

The work was performed at the Institute of Optics atmosphere of the Siberian Branch of the Russian Academy of Sciences

Scientific leader: - Doctor of Physical and Mathematical Sciences

professor, Corresponding Member of RAS Zuev Vladimir Vladimirovich

Official opponents: - Doctor of Physical and Mathematical Sciences

professor Sorochin Igor Anatolyevich. - Candidate of Physical and Mathematical Sciences Senior Researcher Prokopyev Vladimir Egorovich.

Leading organization: Tomsk Polytechnic University

The defense will take place "December 15" December 2004. at 14 h. 00 min. At the meeting of the dissertation council D 212.005.03 at the Altai State University at the address: 656049, Barnaul, Lenin Ave., 61

The dissertation can be found in the library of the Altai State University.

Scientific Secretary

dissertation council K.F-M.N.

DD Ruder

Relevance of the topic. Under the influence of various factors, the environment undergoes changes. The rapid development of industry, energy, agriculture and transport leads to an increase in anthropogenic environmental impact. A number of harmful by-products in the form of aerosols, gases, waste household and technical waters, petroleum products, etc., comes to the atmosphere, hydrosphere and lithosphere in the atmosphere, and soils. Therefore, the actual problem of modernity is environmental control.

Currently, chemical, thermal, electrical, chromatographic, mass spectral and optical gas analyzers are used to control the state of the atmosphere. Moreover, only the latter are non-contact, they do not require sampling, which makes additional errors in the measurable value. A special place among optical methods of gas analysis belongs to laser methods, which are inherent in: high concentration sensitivity of measurements and spatial resolution, remoteness and speed. First of all, it concerns laser gas analyzers working on the effect of resonant absorption, which has the greatest cross-section of the interaction of optical radiation with the medium under study, which ensures maximum sensitivity. Such gas analyzers are implemented, as a rule, a differential absorption scheme. With the development of laser technology in our country and abroad, the development of optical-acoustic (for local gas analysis) and tracks (giving integral values \u200b\u200bof the concentrations of the gas study) laser gas analyzers, as well as lidars (Lidar- abbreviation from English words Light Detection and Ranging), giving Information on the concentration of gases in the atmosphere with spatial resolution. But for the period of the beginning of work on the dissertation, with a rare exception, all of them were laboratory layouts designed to measure one, the maximum of two gas components, while environmental monitoring requires multicomponent gas analysis.

All gas components of the atmosphere of land except the main: nitrogen, oxygen, and argon, are considered to relate to the so-called small gas component (MGS). The percentage of the MGS in the atmosphere is not enough, but the growth of their content due to the anthropogenic factor has a significant impact on many processes occurring in the atmosphere.

As is clear from literary sources, for the purposes of laser gas analysis of the MGS, the average IR region of the spectrum is most suitable. Here are the main vibrational rotational stripes of most MGS, which have permitted structures. In this area, high-energy molecular lasers emit, including reliable and efficient CO and CO2 lasers. For these lasers, highly efficient parametric frequency converters (PPC) have been developed, which allow you to close enough to overlap the emission lines

awable spectral int transparency atmosphere

Simioteka I.

spheres. Another informative spectral range for laser gas analysis is UV region. Here are the strong electronic bands of many polluting gases. In contrast to the middle IR region of the UV spectrum, the absorption band is non-selective and mutually recreated. The greatest development in this area was the ozonometric method due to the presence of the absorption bands of Hartley Haggins ozone.

Purpose of work. Development based on the differential absorption method of gas analyzers for detecting and measuring the concentrations of the MGS and the determination of their spatial-temporal distribution in the atmosphere.

The following tasks were performed during the work:

Creating a channel sensing channel of the vertical distribution of ozone (VRO) in the stratosphere (based on the receiving mirror 0 0.5 m) on the Siberian Ladar Station (SLS);

Control of the state of the ozoneosphere in routine measurement mode;

The study of the climatology of the ozoneosphere, the assessment of the trends of the stratospheric ozone.

The defense takes place:

2. Developed Laser Gas analyzers of the Tral series, on average IR spectrum range, allowing you to quickly measure concentrations of more than 12 gases at the level and below the MPC on the tracks up to 2 km long using a mirror or topographic retroreflex.

3. Created by the author of UV ozone lidar based on an excimer XEQ laser, which ensured uninterrupted long-term sounding of the ozoneosphere over Tomsk at the Siberian Ladar Station in the range of 13-45 km high, with a maximum vertical resolution of 100 m.

Scientific novelty of work:

For the first time, informative wavelengths of sensing wavelengths of the MGC of the atmosphere using IR molecular lasers and PPC are selected and experimentally checked;

A number of unique mobile and stationary track gas analyzers have been created, allowing you to quickly carry out a multicomponent analysis of the gas composition of the atmosphere;

Daily moves of the concentration of MGC (such as C2H4, NH3, H2O, CO2, CO, OZ, N0, etc.) were carried out in environmentally friendly and exposed to significant anthropogenic loads of the country's regions;

Using work results. The data obtained by gas analyzes were presented for the USSR Olympic Committee in 1979-1980. In Moscow, as well as in environmental organizations G.G. Tomsk, Kemerovo, Sofia (NRB), entered the final reports of the IOO SB RAS for various grants of the Russian Federation, contracts, contracts and programs, such as "Tor" (tropospheric ozone studies), "SATOR" (stratospheric and tropospheric ozone studies) and others.

The practical value of the work is as follows: -The-acoustic gas analyzer is developed, which makes it possible to measure concentration with high accuracy, as the sums of methane hydrocarbons, and separately methane and heavier hydrocarbons in a mixture of natural and associated petroleum gases. With this gas analyzer, it is possible to search for oil and gas on gas halisters of gases overlooking the surface of hydrocarbons;

The developed track gas analyzers can measure the concentrations of the MGC at the level and below the MPC from a wide list of priority polluting gases;

Create a channel sounding channel of the vertical distribution of ozone ozone on the basis of a mirror 0.5 m, which allows reliable profiles of VRO in the range of 13-45 km high with a maximum resolution of 100 m.

The accuracy of the results of the work is ensured: -Horishable acceptance of the experimental data obtained by the developed gas analyzers, and data obtained at the same time by other methods, as well as; data obtained by other authors in similar climatic and environmental conditions;

A good coincidence of profiles in the stratosphere, measured by Lidar, data of ozoneozonda, as well as satellite measurements within the error of the devices used.

Approbation of work. The main results on the thesis obtained by the author were published in 11 articles in Russian scientific peer-reviewed journals, reported on: VI, VII and XI All-Union Symposia on Laser and Acoustic Sensation (Tomsk, 1980, 1982, 1992); VI All-Union Symposium for the spread of laser radiation in the atmosphere (Tomsk 1881); XII All-Union Conference on Coherent and Nonlinear Optics (Moscow, 1985); V International School-Seminar on Quantum Electronics. Lasers and their use (NRB, Sunny Beach, 1988); 5 Scientific Assembly of the International Association of Atmospheric Physics and Meteorology (Riding, United Kingdom, 1989); XI symposium on laser and acoustic sensing (Tomsk, 1992); And, III, IV and VI inter-republican symposia "Optics of the atmosphere and Ocean" (Tomsk, 1995, 1996, 1997 and 1999); III Siberian Meeting on Climate Ecological Monitoring (Tomsk, 1999); I interregional Meeting "Ecology of Siberian Rivers and Arctic" (Tomsk 1999); VII International Symposium on the optics of the atmosphere and the ocean (Tomsk 2000); VIII and IX International Symposiums for the Optics of the atmosphere and Ocean and atmospheric physics (Tomsk 2001 and 2002); 11 atmospheric radiation measurements (Atlanta, USA 2001); IX Working Group "Siberia Aerosols" (Tomsk 2002); 21 and 22 International Laser Conference (Quebec, Canada, 2002, Matera, Italy 2004); II International Conference "Environment and Ecology of Siberia, the Far East and Arctic" (Tomsk 2003). International Conference on Optical Technologies for Studies of the Atmosphere, Ocean and the Environment (Beijing, China 2004).

Personal contribution. The paper uses the results obtained either by the author personally or in direct participation. This is the participation of the author in the development of both general schemes for the construction of gas analyzers and their individual optical and electronic components and blocks; Conducting assembly and commissioning. Development of measurement techniques, test and expeditionary and field tests created by gas analyzers, also presented in the work, were held with the direct participation of the author. Since 1996, almost all observations of the state of the ozoneosphere on SALS were held with the active participation of the author. It was created an improved channel testing of the vertical distribution of ozone ozone on the basis of the XEQ laser and the receiving mirror 0 0.5 m. The author's reanalysis conducted by the authorized VRO made it possible to determine the features of the ozone-sofosphere climatology on Tomsk ..

The development of IR gas analyzers "LAG-1" and "Resonance-3" was carried out jointly with KF-M.N. G.S. Khmelnitsky, the remaining results were obtained under the guidance of a corresponding member. RAS, D.F-M.N. V.V. Zueva with the participation of employees of his laboratory at different stages of work.

In the introduction, the relevance of the topic is justified, the objectives and objectives of the study are formulated, scientific novelty and practical significance are underlined, the main provisions submitted to protection are underlined.

The first chapter describes the optical acoustic method, the flowchart of an optical-acoustic gas analyzer intended for separate measurement of methane concentrations and other limiting hydrocarbons in air samples.

Numerous studies have shown the presence of elevated concentrations of hydrocarbons (HC) in the atmosphere and samples of soil air over the areas of oil and gas deposits. The authors expressed the opinion that this is due to the yield of HC from deposit to the day surface. In these facts, geochemical methods for finding oil and gas deposits are based. According to the percentage (by volume), the composition of natural gases of the former USSR deposits: methane 85-95%; Ethan up to 7%; propane up to 5%; Bhutan up to 2%; Pentan and heavier HC to 0.4%. Composition of oil associated gases of oil and gas fields: methane up to 80%; Ethan up to 20%; propane up to 16%; isobutane + n-butane to 6%; Pentanes and heavier WCs up to 0.9%. Thus, pentanes and heavier hydrocarbons make a minor contribution to the content of gas halisses over oil and gas fields.

Fig. 1. Flow diagram of gas analyzer 1- 2-C g Laser with a diffraction grid ;; 4, 5- non-laser; 7, 9, 10-formation of impulses; 8 modulator; 11- modulator control unit; 12-chamber spectrophone; 13 mspochon; 14-selective amplifier; 15- ADC!; 16-frequency meter; 17-attenuator; 18-receiver; 19-electronic clock; 20-АЦП2; 21- control unit; 22-micro-computer; 23-digital.

When searching for oil and gas fields over gas halisters overlooking the fields of hydrocarbons of hydrocarbons, it is of great importance to a separate measurement of methane concentration and heavier HC, since methane can be a product of not only deep structures, but also the upper biologically active layers and not always be the forerunner of the field . This is characteristic, for example, for

padinal Siberia, where methane can be generated in large quantities of swamps located on its territory, while heavy hydrocarbons in the upper layers of the earth's crust are not generated. The paper analyzes the possibility of such a separate measurement, provided that in the mixtures, methane content is not more than 100 times higher than the content of other HC.

The highly sensitive optical-acoustic gas analyzer "LAG-1" allows you to register concentrations in in with any ratio of a mixture of methane and other HC. The flowchart of the gas analyzer is presented in Fig. one.

The gas pressure in the cylindrical spectrophone chamber (optical-acoustic detector) When passing through it, the modulated laser radiation at the modulation frequency of the CO radiation frequency depends on the power of the laser radiation and the absorption coefficient of the AOR gas and the quality frequency of the acoustic resonator at the Q (CO) modulation frequency as:

5 BG02 [CO2 + T1) "

where £) is a cylinder -diameter; TG Temperature Relaxation Spectrophone.

Pressure pulsations are converted to an electrical signal with a condenser microphone type MKD / MV 101 (13). Further, the signal is enhanced by selective amplifier of type U2-8 (14), the ADC1 (15) is digitized and enters the results processing system. The laser radiation passed through the camera spectrophone is weakened by the attenuator (17), it falls on the thermoelectric receiver (18), the ADC2 (20) is digitized and also enters the results processing system

The system calculates the absorption coefficients:

and gas concentration in the case of prevailing absorption in single channel:

/ \u003d /, 2, 3 ... p,

where the L-coefficient of calibration of the spectrophone; p-exchange measurements; £ / s /-Signal from the microphone; - signal, proportional power of laser radiation; - background signal spectrophone; Mass absorption coefficient by gas test. The result of the calculation together with the wavelength code and time is displayed on digital.

In the area of \u200b\u200brearrangement of the sh-laser, the radiation line at a wavelength of 1.15 μm coincides with the absorption line by water ferry of the atmosphere, and the line 3.39 μm-with the absorption band of the methane group hydrocarbons, starting from methane. In the area of \u200b\u200brestructuring the wavelength of the CO2 laser (9.1-10.8 μm) there are uv absorption bands, starting with

this, thus, having measured the concentrations of the amount of hydrocarbons and separately ethane, propane and butane becomes possible to determine the concentration of methane. Table 1 shows a list of these gas components, their absorption coefficients on the respective wavelengths of radiation waves and SO2 lasters:

Table 1

Gas non-mea x. \u003d 3.39mkm A, see "1 atm" 1 C02

A, μm A, see "1 atm" 1

Methane 9.0 - - -

Ethan 4.1 10,8847 0.5

Propane 9.0 10,8352 0.45-0.5

N-butane 12.6 10,4762 0.9

Isobutan 13 10,8598 0.4

Due to the fact that the CO2 laser has a wide range of restructuring, it is possible to separately measure the ethane, propane, n-butane, isobutane, ethylene and benzene and other gas components. From the same table, it can be seen that the absorption coefficients of the CO2 laser radiation hydrocarbons are 10-20 times smaller than the radiation coefficients of the radiation of the W-N-laser. But for a resonant spectrophone, the sensitivity is proportional to the power of laser radiation passing through it (formula 1), and then at the LG-126 type laser power at length

waves of 3.39 μm 8 MW, and a CO2 laser 10 W This gas analyzer has a sensitivity 100 times higher in heavy HC.

Figure 2 presents the results of comparative measurements of the HC obtained during one of the expeditions along the river of the OU more different gas analyzers: LAG-1 (measured both the amount of HC with methane and separately heavier HC), "seeker" (the amount of HC with methane was measured ) and the SCR-Lidar (the amount of HC without methane was measured). The data obtained by all these devices suggest a sharp increase in the content of the HC in the atmosphere above the fields of oil and gas.

Distance hm.

Fig. 2. The concentration of hydrocarbons for measurements of different gas analyzers

Away from the fields of concentration of ethane, propane and butane not

exceeded 0.02 million "1, methane-1.7-2 million" 1, but as the concentration of heavier hydrocarbons approached the explored fields as the concentration of heavier hydrocarbons approached. For example, in the area of \u200b\u200bthe oil field in the lower reaches of the River Vakh (point 650 km in fig. 2.) The following concentrations were measured: the sum of 5.1 million "1, ethano-1.0 million" 1, propane-1.7 million "1, butane-0.3 million" 1, with a concentration of methane 2.1 million "1. Thus, it can be seen that with relatively small variations of methane concentration in the atmosphere (1.5-2.0 million 1), The large values \u200b\u200bof the amount of hydroelectric deposits of oil and gas are obliged to increased concentrations of heavy HC.

The test tests have shown the good performance characteristics of the Lag-1 gas analyzer in the field. The results obtained with its help are well consistent with the results obtained on other measuring systems during the joint measurements, show their accuracy. The use of two laser sources in the complex (non-CO2) and spectrophone allows you to measure the concentration of a wide range of both atmospheric and polluting gas atmosphere. Which is especially important, it is possible to separately measure the methane fraction and heavier hydrocarbons in a mixture of natural and associated gas. This makes it possible to hope for the use of the proposed gas analyzer to search for oil and gas fields over gas halisters of hydrocarbon land, as well as for the operational analysis of the core gas fraction during exploration drilling of wells.

The second chapter provides a description of a series of track gas analyzers "Resonance-3", "Truble", "Tral-3", "Tral-ZM", "Tral-4" working on the basis of the method of differential absorption (DP) summarizes the method itself.

The power of the optical signal taken during i, at the DP trace method for one wavelength x can be recorded in the form:

where R - - transmitted optical power (W),

g is the distance (cm), the speed of light - 3 x y.10 cm / s,

P, (g) ~ Total optical efficiency of the transmitter,

<т,- поперечное сечение поглощения (см2),

Apecus aperture (cm2),

a (g) - the attenuation coefficient (see "1),

I, - body scattering angle back targets (cf "1),

/ "- wavelength index, / \u003d / and 2, for wavelengths at maximum and minimum absorption, respectively, N0- gas concentration (see" 3).

For two close wavelengths fairly:

Then the average gas concentration in the volume under study can be expressed as follows, as well as lidars (lidar-abbreviation from English words Light Detection and Ranging), giving information with a space-time resolution to study the MGC concentration in the atmosphere. But for the period of the beginning of work on the dissertation, with rare exceptions, all of them were calculated on measuring one, the maximum of two gas components, or were laboratory layouts, while environmental monitoring requires multicomponent gas analysis to sufficiently extended highways (along the city highways, territory large industrial enterprises).

As is clear from literary sources for the purposes of laser gas analysis MGS, the average IR region of the spectrum is most suitable. Here are the main vibrational and rotational stripes of most MGS. There are permitted structures and individual absorption lines of almost all atmospheric gases except for simple, type N2, O2, H2.

On average IR - the range of spectrum, as is known, highly efficient molecular lasers radiate: CO, CO2, NH3, HF, DF and others. Of these, highly efficient Sog-Lasers are the most reliable and acceptable for the purposes of gas analysis. In these lasers, in addition to traditional strips 9.6 and 10.6 μm, sequenced strips are shifted relative to the traditional approximately 1 cm "1, as well as the main strip of 4.3 μm and hot radiation lines. If we consider what is possible And CO2 isotopes to obtain an additional set of shifted generation lines, we will get a rich set of radiation lines for this laser source.

Recently developed highly efficient parametric frequency converters based on nonlinear crystals ZNGEP2, CDGEAS2, TLASSE3, AGGASE2, etc. allowed to obtain the second, third and fourth harmonics of the radiation of the Sog laser, as well as the total difference frequencies of two CO2 and other lasers, such as , NH3, erbium, etc. For laser probing of atmospheric MGS, it is important that most of these emission lines, including converted, fall into the spectral windows of the atmosphere transparency.

Thus, a low pressure molecular CO2 laser, equipped with a set of unless parametric frequency converters from ZNGEP2, CDGEAS2, TLASSE3 and AgGaSe2, satisfies most of the following requirements. The distance between adjacent lines of such lasers is approximately 1.5-2 cm "1, which simplifies the problem of spectral selection and restructuring them in frequency. Using a two-stage conversion, for example, a CO2 of the laser or the total-difference frequencies of two C02, or CO2 and the lakes. And their harmonics, it is possible very tight, with a step to Yu ^ cm "1, overlap the range from 2 to 17 microns. The position of the centers of the pump laser radiation lines and a fairly narrow spectral width (2x 10 "3 cm" 1) is provided by the physical parameters of the active medium. The position of the lines centers, and, consequently, the position of the radiation lines of the transformed frequencies are known with very high accuracy, which removes the problem of controlling spectral characteristics. The effectiveness of such converters is sufficiently high and ranges from tenths to dozen percent, which allows you to create track gas analyzers using topographic objects and atmospheric aerosols as reflectors.

Another informative spectral range for laser gas analysis is UV region. Here are the strong electronic bands of many polluting gases. In contrast to the middle IR region of the UV spectrum, the absorption band is non-selective and mutually recreated. The greatest development in this area was the ozonometric method due to the presence of the absorption bands of Hartley Haggins ozone.

The ability to perform spatially permitted measurements of atmospheric ozone Lidar was first shown in 1977 (inext, etc.). And, since the second half of the 80s of the last century, the laser sensing of the ozoneosphere has acquired a regular character on a number of observatory. It provides information on the vertical distribution of ozone (VRO), successfully complementing such information obtained by the contact method using ozoneozondes and rockets, especially above 30 km, where the data of ozoneozonds become unrepresentative.

In the Siberian Ladar Station, observation of the ozoneosphere is conducted from December 1988. During this period, the lidar technique was constantly improved, the method of measurement and data processing was developed and improved, software was created to control the measurement process, new packages of processing programs obtained.

Purpose of work. Development based on the differential absorption method of gas analyzers for detecting and measuring the concentration of MGS and determine their spatial-temporal distribution in the atmosphere.

The following tasks were performed during the work;

Development of an optical acoustic gas analyzer for local gas analysis and a study with the help of a spatial distribution of hydrocarbons and other MGS;

Development and creation of trail laser gas analyzers for the study of the gas composition of the atmosphere;

Development of methods for measuring MGS in the atmosphere;

Home-based tests of developed devices based on the developed measurement methods;

Study of the temporal dynamics of the MGS in environmentally friendly and exposed to significant anthropogenic load regions of the country;

Creating a channel sensing channel of the vertical distribution of ozone (VRO) in the stratosphere (on the basis of the receiving mirror 0 0.5 m) CJIC;

Control of the state of the ozoneosphere in routine measurement mode; -Investment of the climatology of the ozoneosphere, the assessment of the stratospheric ozone trends.

The defense takes place:

1. The developed laser optical-acoustic gas analyzer "LAG-1", which allows the method of the created method to separately measure the concentrations of methane and heavier hydrocarbons in air mixtures of natural and associated gas with any ratio of the component in the mixture.

2. Developed Laser Gas analyzes of the Tral series, on average IR spectrum range, allowing you to quickly measure concentrations of more than 12 gases at the level and below the MPC on the tracks up to 2 km long using a mirror or topographic retroreflector.

3. Created by the author of UV ozone lidar based on an excimer hies1 laser, which ensured uninterrupted long-term sensing of the ozoneosphere over Tomsk at the Siberian Ladar Station in the range of 13-45 km high, with a maximum vertical resolution of 100 m.

Scientific novelty of work.

For the first time, informative wavelengths of the sensing wavelength of the MGC of the atmosphere are chosen and experimentally.

A number of unique mobile and stationary trail gas analyzers were created on the basis of tunable molecular lasers with radiation frequency converters, allowing you to quickly carry out a multicomponent analysis of the gas composition of the atmosphere;

Daily moves of the concentration of MGC (such as C2H4, NH3, H2O, CO2, CO, O3, N0, etc.) were carried out in environmentally friendly and exposed to significant anthropogenic loads of the country's regions;

The climatological features of the ozoneosphere above Tomsk are determined on the basis of regular and long-term measurements of the profiles of the vertical distribution of ozone;

Using work results. The data obtained by gas analyzes were presented for the USSR Olympic Committee in 19791980. In Moscow, as well as in environmental organizations G.G. Tomsk, Kemerovo, Sofia (NRB). They entered the final reports of the IOO SB RAS for various grants of the RFBR, contracts, contracts and programs, such as "Tor" (Torpospheric Ozone Research), "Sator" (stratospheric and tropospheric ozone studies) and others.

The practical value of the work is as follows:

An optical-acoustic gas analyzer was developed, which makes it possible to measure concentration with high accuracy, as the sums of the methane group hydrocarbons and separate methane and heavier hydrocarbons in a mixture of natural and associated gas gases. With this gas analyzer, it is possible to search for oil and gas on gas halisters of gases overlooking the surface of hydrocarbons;

The developed track gas analyzers can measure the concentrations of the MGC at the level and below the MPC from a wide list of priority polluting gases;

A channel sensing channel of the vertical distribution of CJIC ozone based on the receiving mirror is 0 0.5 m, which allows to obtain reliable profiles of VRO in the range of 13-45 km with a maximum resolution of 100 m.

The accuracy of the results of the work is ensured: -Horishable acceptance of the experimental data obtained by the developed gas analyzers, and data obtained at the same time by other methods, as well as; data; obtained by other authors in similar climatic and environmental conditions;

A good coincidence of the profiles in the stratosphere measured by Lidar, database of ozoneozondov, as well as satellite measurements within the error of the devices used | (fifteen %).

Personal contribution. The paper uses the results obtained either by the author personally or in direct participation. This is the participation of the author in the development of both general schemes for the construction of gas analyzers and their individual optical and electronic components and blocks, assembling and commissioning. Development of measurement techniques, test and expeditionary ^ and field tests of the created gas analyzers, also presented in the work, were held with the direct participation of the author. Since 1996, almost all observations over the state of the ozoneosphere on CJIC passed with the active participation of the author. They created an improved channel sensing channel of the vertical distribution of CJIC ozone on the basis of the xen laser and the receiving mirror 0 0.5 m. The author's reanalysis conducted by the author.

The process of developing gas analyzers, their test tests, processing the results obtained during forwarding work, many years of accumulation of such a larger amount of empirical information on VRO and its analysis could not be implemented without the active participation of a whole team, without which this dissertation work would not take place. The task and scientific leadership at different stages were carried out by CC. RAS Zuevov V.V. And K.F-M.N. Khmelnitsky G.S. The development of gas analyzers and their test and field tests were carried out in conjunction with D.F-M.N. Andreyev Yu.M., D.F-M.N. Gaiko P.P., Researcher Subin S.F. Theoretical works on the search for informative wavelengths were made by a d.N. MICETER A.A., D.F-M.N Kataev M.Yu., K.F-M.N. Ptashnik I.V., K.F-M.N. Romanovsky O.A. Ladar measurements of VRO were carried out jointly by S.N. Nevzorov A.V., K.F-M.N. Burlakovov V.D. and D.F-M.N. Marichev, V.N., and processing data sensing together with K.F-M.N. Bondarenko cl. and D.F-M.N. Ylannikom A.V.

Approbation of work. The main results on the thesis obtained by the author were published in 11 articles in Russian scientific peer-reviewed journals, reported on: VI, VII and XI All-Union Symposia on Laser and Acoustic Sensation (Tomsk, 1980, 1982, 1992); VI All-Union Symposium for the spread of laser radiation in the atmosphere (Tomsk 1881); XII All-Union Conference on Coherent and Nonlinear Optics (Moscow, 1985); V International Ceases: I am a seminar on quantum electronics. Lasers and their use (NRB, Sunny Beach, 1988); 5 Scientific Assembly of the International Association of Atmospheric Physics and Meteorology (Riding, United Kingdom, 1989); XI symposium on laser and acoustic sensing (Tomsk, 1992); And, III, IV and VI inter-republican symposia "Optics of the atmosphere and Ocean" (Tomsk, 1995, 1996, 1997 and 1999); III Siberian Meeting on Climate Ecological Monitoring (Tomsk, 1999); I interregional Meeting "Ecology of Siberian Rivers and Arctic" (Tomsk 1999); VII International Symposium on the optics of the atmosphere and the ocean (Tomsk 2000); VIII and IX International Symposiums for the Optics of the atmosphere and Ocean and atmospheric physics (Tomsk 2001 and 2002); 11 atmospheric radiation measurements (Atlanta, USA 2001); IX Working Group "Siberia Aerosols" (Tomsk 2002); 21 and 22 International Laser Conference (Quebec, Canada, 2002, Matera, Italy 2004); II International Conference "Environment and Ecology of Siberia, the Far East and Arctic" (Tomsk 2003); International Conference on Optical Technologies for Studies of the Atmosphere, Ocean and the Environment (Beijing, China 2004).

Structure and scope of the dissertation. The dissertation work consists of introduction, three chapters and conclusion. The amount of the dissertation of 116 pages, it contains 36 drawings, 12 tables. The list of references used contains 118 items.

Conclusion of dissertation on "Devices and methods of experimental physics"

Conclusion

In the course of the dissertation work, the author as part of the team was done as follows:

An optical-acoustic gas analyzer for local gas analysis was developed, with its help a study of the spatial distribution of the hydrocarbons (during several expeditions on the motor ship) in areas where oil deposits are located. The measured increase in the content of hydrocarbons in air samples in the area of \u200b\u200boil deposits confirmed the hypothesis about the presence of gas halisols over hydrocarbon fields and the prospects for the use of this gas analyzer to search for oil and gas deposits;

A complex of trace laser gas analyzers operating in the IR region of the spectrum on the differential absorption method and allowed to measure concentrations of more than 12 gases at the level and below the MPC;

The method of measuring MGS in the atmosphere is worked out;

Western tests of the developed devices were carried out;

Experimentally, a pair of informative wavelengths and conclusions were made about their suitability for the purposes of gas analysis on TIR;

There are studies of the time dynamics of the MGS in environmentally friendly and exposed to significant anthropogenic loads of the country's regions;

Comparative measurements were carried out by the concentrations of MGS developed by laser gas analyzers and devices working on the basis of standard methods, which showed good agreement of the results obtained;

A channel of probing the vertical distribution of ozone (VRO) was created in the stratosphere (based on the receiving mirror 0 0.5 m) CJIC, which provided during a multi-year period of time to obtain reliable profiles VRO over Tomsk confirmed by well-consistent with satellite and ozone-visual data. This allowed climatological studies and evaluate the trends of stratospheric ozone, which showed that in the lower stratosphere at heights below 26 km. . At an altitude of 26 km, in the area of \u200b\u200bwhich there is a blessing, the ozoneosphere is divided into two parts: at the bottom of its behavior is determined mainly by dynamic processes, and at the top - photochemical. A more detailed consideration of intra-cost changes, it allows to distinguish the following points: a) at an altitude of 14 km, where, apparently, the effect of the fluctuations of the height of the tropopause, no localized maximum is observed; b) in the range up to 18 km inclusive, the maximum of seasonal oscillations falls in February, and in the range of 20-26 km - by March; The greatest compliance of the in-year changes to the OSO annual movement is observed in the high-voltage range of 20-24 km, especially at an altitude of 22 km. c) At all altitudes, the trends of the VRO were statistically insignificant. At the same time, in the lower part of the ozoneosphere, they are characterized by weakly negative values, and in the upper - weakly plane. In the area of \u200b\u200blocalization of the stratospheric ozone maximum 20 km), the values \u200b\u200bof negative trends are small (-0.32% per year). These results are consistent with a minor statistically insignificant SPO trend (0.01 + 0.026% per year) for the same six-year period.

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The effect of the laser gas analyzer Yokogawa TDLS200 is based on the method of diode laser absorption spectroscopy.

This device is characterized by high selectivity and long-term stability, provides a quick "in-situ" (directly in the pipe) analysis of gases with corrosive-aggressive components or high temperatures. What is the principle of operation of this device and where does it find its application?

The laser gas analyzer uses the method of absorption spectroscopy based on a tunable laser diode (TDLAS) and has the ability to measure the concentration in the sample of gas with high selectivity and without direct contact - only by irradiating the gas sample radiation by the radiation of the rebuilt laser diode. Thus, fast and accurate "In-situ" can be performed in the process of the technical process under various conditions. For example, measurements can be carried out at temperatures up to 1500 ° C, as well as in fluids with pulsating pressure. The laser gas analyzer Yokogawa TDLS200 can also measure with corrosive-aggressive or toxic gases. Accurate analytical signals formed by the analyzer have a minimum response time, which contributes to an increase in product output, increases energy efficiency and safety in various production technological processes. The simplicity of design (the lack of moving parts and components with a limited service life) guarantees operation and management of almost no maintenance.

Laser gas analyzer Yokogawa TDLS200 is a new type of laser gas analyzers used for industrial measurements. The use of the method of integration of the peak area eliminates measurement errors caused by a change in pressure and the presence of other gases in the sample. It also allows you to accurately determine the concentration of gas components, even while simultaneously changing its temperature and other indicators. This article represents an overview of the TDLS200 laser gas analyzer, its functions and measurement principle, and also considers examples of its application.

The gas analyzer has a radiation unit and a detection unit, which is usually placed opposite each other on opposite sides (across) of the gas pipe, through which the gas flow of the technical process. Such an option is used for gas ducts up to 20 m wide.

Optical windows are separated by the internal parts of the analyzer from the measured medium. The radiation of the semiconductor laser passes through the optical window of the radiation unit, the measured gas, the optical window of the detection block and reaches the photodetector. A photodetector registers a laser beam and converts its energy into an electrical signal. The emission unit computing device defines the absorption spectrum of the measured component, calculates the peak area of \u200b\u200bthe spectrum, converts it to the component concentration and displays 4 ... 20 mA as an analog signal.

The adjustment mechanism has a corrugated structure, which allows you to simplify the angle adjustment of the angle of the optical axis, while maintaining the tightness of the pipeline, which is especially important for technological processes in the industry. The connection of the radiation block and the detection unit using the optical axis adjustment device simplifies the optical axis setting not only for the standard configuration, (two blocks are placed on both sides of the pipe, as shown in Figure 1), but also for other installation options. This technical solution allows you to choose the method of installing the device that is best suited for measured components and process design of the process, and at the same time guarantees optimal measurement conditions.

TDLS200 uses a diode laser absorption spectroscopy (TDLAS) method. The method is based on measuring the radiation absorption spectrum (infrared / near infrared), characteristic of the substance molecules due to the oscillatory and rotational energies of the transition of molecules in the measured component. The radiation source for the formation of the spectrum is a semiconductor laser with an extremely narrow spectral line width. The optical absorption spectrum peculiar to the main molecules, such as O2, NH3, H2O, CO and CO2, is located in the region from infrared to neighboring infrared. Measuring the magnitude of the absorbed radiation at a certain wavelength (spectral absorption capacity) makes it possible to calculate the concentration of the measured component.

In contrast to conventional low-resolution spectrometers, TDLS200 uses a laser beam with an extremely narrow spectral line width. The emitter is the rebuilt laser diode, the radiation wavelength of which can be changed by adjusting the laser temperature and excitation current. This allows you to measure a single absorption peak from several present in the spectrum. Thus, as shown in Figure 6, one absorption peak can be selected for measurement, which is not subjected to interference from other gases.

Due to the high selectivity in the wavelength and the absence of interference from other components in the gas mixture, there is no need for additional sample preparation, which allows the use of TDLS200 "in-situ" (directly during process).

TDLS200 measures the separate absorption spectrum of the component of the gas mixture, free from the influence of interfering components. The measurement is carried out by expanding the wavelength of the tunable laser diode along a single peak of the absorption of the measured component.

Although the absorption spectrum measured by the TDLS200 is isolated from interfering components, the form of the spectrum may vary (expansion effect) depending on the gas temperature, the gas pressure present in the gas mixture of third-party components. For measurements in such conditions requires compensation.

The TDLS200 gas analyzer exercises a wavelength of the radiation wave of a semiconductor laser along the absorption line of the measured component and calculates its concentration over the spectral absorption area by the method of integrating the peak area.

Yokogawa TDLS200 gas analyzer Thanks to the possibility of a quick measurement of "In-situ" (directly in the pipeline), it can be successfully applied to active technical processes as for high-speed controls when the signals that are required to control the signals that contain the testimony of the component concentrations are fed directly to the RSU and for Control of the status of the technical process in real time. Thus, the TDLS200 may contribute to the optimization of indicators of various industrial process machines. In this section, we will look at the measurement of the residual concentration of NH3 in the smoke gas. Please note that the use of TDLS200 to optimize the combustion process was described in another article of the company Yokogawa (3). For more information, refer to this report.

Ammonia (NH3) is introduced into the flue gas in order to remove NOx (cleaning outgoing gases from nitrogen oxides), increase the efficiency of dust collectors and corrosion prevention. Excess NH3 enhances operating costs and the amount of residual NH3, leading to the appearance of a rotor odor. Thus, the amount of NH3 in exhaust gas must be measured, monitored and adjust. For example, in the exhaust gas cleaning equipment, the DENOX ICV process (selective catalytic recovery) is used in nitrogen oxides (selective catalytic recovery), in which NOx is reduced to N2 and H2O using the NH3 injection and the selective catalysis of the recovery process, and the residual concentration of NH3 (PPM order) in flue gases is measured in real time.

Traditional devices for measuring NH3 concentration using indirect measurement methods NOX (chemiluminescent analysis and ion-electrode method) have a great response time, require a sampling line setting, including heated pipes to avoid NH3 adhesion, and, accordingly, high maintenance costs Such complex measuring systems. On the other hand, as shown in Figure 8, the TDLS200 laser gas analyzer is installed directly into the process pipeline and measures NH3 directly, which significantly reduces the response time and simplifies the maintenance. In addition, the analytical signal of the NH3 concentration with a rapid response can be involved to regulate and optimize the NH3 injection.

High selectivity, small response time, simplicity of maintenance, achieved thanks to the measurement technology used and the constructive execution of the analyzer, provide the possibility of applying it in a wide range of technological processes. Application options include not only the measurement of NH3, considered in this article, but also determining the content of CO and O2 in optimizing the combustion processes, measurement of the small amount of water at the installations of electrolysis, etc. The use of such gas analyzers can make a significant contribution to the preservation of the environment and reducing operating costs Thanks to its application to manage technological processes, and not only for the purpose of monitoring.

Casuto Tamura,

Yukihiko Takamatsu,

Tomoyaki Nanko,