Application of wavelength-scanned wavelength-modulation spectroscopy H2O absorption measurements in an engineering-scale high-pressure coal gasifier

A real-time, in situ water vapor (H₂O) sensor using a tunable diode laser near 1,352 nm was developed to continuously monitor water vapor in the synthesis gas of an engineering-scale high-pressure coal gasifier. Wavelength-scanned wavelength-modulation spectroscopy with second harmonic detection (WMS-2f) was used to determine the absorption magnitude. The 1f-normalized, WMS-2f signal (WMS-2f/1f) was insensitive to non-absorption transmission losses including beam steering and light scattering by the particulate in the synthesis gas. A fitting strategy was used to simultaneously determine the water vapor mole fraction and the collisional-broadening width of the transition from the scanned 1f-normalized WMS-2f waveform at pressures up to 15 atm, which can be used for large absorbance values. This strategy is analogous to the fitting strategy for wavelength-scanned direct absorption measurements. In a test campaign at the US National Carbon Capture Center, the sensor demonstrated a water vapor detection limit of ~800 ppm (25 Hz bandwidth) at conditions with more than 99.99 % non-absorption transmission losses. Successful unattended monitoring was demonstrated over a 435 h period. Strong correlations between the sensor measurements and transient gasifier operation conditions were observed, demonstrating the capability of laser absorption to monitor the gasification process.     

Wavelength-modulation-spectroscopy for real-time, in situ NO detection in combustion gases with a 5.2 μm quantum-cascade laser

A mid-infrared absorption strategy with calibration-free wavelength-modulation-spectroscopy (WMS) has been developed and demonstrated for real-time, in situ detection of nitric oxide in particulate-laden combustion-exhaust gases up to temperatures of 700 K. An external-cavity quantum-cascade laser (ECQCL) near 5.2 μm accessed the fundamental absorption band of NO, and a wavelength-scanned, 1f-normalized WMS with second-harmonic detection (WMS-2f/1f) strategy was developed. Due to the external-cavity laser architecture, large nonlinear intensity modulation (IM) was observed when the wavelength was modulated by injection-current modulation, and the IM indices were also found to be strongly wavelength-dependent as the center wavelength was scanned with piezoelectric tuning of the cavity. A quantitative model of the 1f-normalized WMS-2f signal was developed and validated under laboratory conditions. A sensor was subsequently designed, built and demonstrated for real-time, in situ measurements of NO across a 3 m path in the particulate-laden exhaust of a pulverized-coal-fired power plant boiler. The 1f-normalized WMS-2f method proved to have better noise immunity for non-absorption transmission, than wavelength-scanned direct absorption. A 0.3 ppm-m detection limit was estimated using the R15.5 transition near 1927 cm⁻¹ with 1 s averaging. Mid-infrared QCL-based NO absorption with 1f-normalized WMS-2f detection shows excellent promise for practical sensing in the combustion exhaust.     

Wavelength-modulation spectroscopy near 2.5 μm for H2O and temperature in high-pressure and -temperature gases

The design and validation of a tunable diode laser (TDL) sensor for temperature and H₂O in high-pressure and -temperature gases are presented. High-fidelity measurements are enabled through the use of: (1) strong H₂O fundamental-band absorption near 2.5 μm, (2) calibration-free first-harmonic-normalized wavelength-modulation spectroscopy with second-harmonic detection (WMS-2f/1f), (3) an experimentally derived and validated spectroscopic database, and (4) a new approach to selecting the optimal wavelength and modulation depth of each laser. This sensor uses two TDLs near 2,474 and 2,482 nm that were fiber coupled in free space and frequency multiplexed to enable measurements along a single line-of-sight. The lasers were modulated at 35 and 45.5 kHz, respectively, to achieve a sensor bandwidth of 4.5 kHz. This sensor was validated in a shock tube at temperatures and pressures ranging from 1,000 to 2,700 K and 8 to 50 bar. There the sensor resolved transients and recovered the known steady-state temperature and H₂O mole fraction with a precision of 3.2 and 2.6 % RMS, respectively.     

Multi-species laser absorption sensors for in situ monitoring of syngas composition

Tunable diode laser absorption spectroscopy sensors for detection of CO, CO₂, CH₄ and H₂O at elevated pressures in mixtures of synthesis gas (syngas: products of coal and/or biomass gasification) were developed and tested. Wavelength modulation spectroscopy (WMS) with 1f-normalized 2f detection was employed. Fiber-coupled DFB diode lasers operating at 2325, 2017, 2290 and 1352 nm were used for simultaneously measuring CO, CO₂, CH₄ and H₂O, respectively. Criteria for the selection of transitions were developed, and transitions were selected to optimize the signal and minimize interference from other species. For quantitative WMS measurements, the collision-broadening coefficients of the selected transitions were determined for collisions with possible syngas components, namely CO, CO₂, CH₄, H₂O, N₂ and H₂. Sample measurements were performed for each species in gas cells at a temperature of 25 °C up to pressures of 20 atm. To validate the sensor performance, the composition of synthetic syngas was determined by the absorption sensor and compared with the known values. A method of estimating the lower heating value and Wobbe index of the syngas mixture from these measurements was also demonstrated.     

Apodized 2f/1f wavelength modulation spectroscopy method for calibration-free trace detection of carbon monoxide in the near-infrared region: theory and experiment

We introduce the basics of an apodized 2f/1f wavelength modulation method for the spectroscopy of the R(9) transition line in the first overtone band of carbon monoxide (¹²C¹⁶O) in near-infrared (NIR) region around 2.33 μm. Performance of the method is investigated for high gas concentrations beyond the optically thin limit to generalize common 2f/1f wavelength modulation spectroscopy (WMS) reported by Rieker et al. (Appl Opt 48:5546, [28]). Numerical simulations are performed based on real experimental parameters associated with a NIR spectrometer designed in our laboratory. The results primarily show a more linear response and less error than occurred in the common WMS-2f/1f method for an optically thick sample. It is also theoretically shown that the apodized method enables sharpening the spectrum without peak displacement compared to the common WMS-2f/1f method. The validity of the method is verified experimentally by the trace detection of an air-broadened R(9) CO absorption line centered at 4,294.637 cm^?1 at atmospheric pressure and room temperature. The effect of a so-called scaling k-factor on the sharpening of WMS-2f/1f signal is investigated through trace simulation and detection of CO and methane (CH₄) lines in the scanning range of a distributed feedback laser. The obtained results show very good agreement between simulation and experiment.     

Characterization of lineshape structure by wavelength modulation spectroscopy

Wavelength Modulation Spectroscopy (WMS) is performed in the oxygen A-band at different harmonics for different modulation indices and optical pathlengths. The experimental data is compared to two models with different absorption profiles: one assuming a Lorentzian lineshape function and the other with a Voigt lineshape function. We show that the larger amount of structure in higher harmonic signals provides greater sensitivity to the type of lineshape profile utilized for modeling. A useful new feature explored in this work is optical path length saturation in WMS that was described for the first time in a recent paper from our group. We discuss the role of such saturation and how it can be utilized as a diagnostic to probe lineshape. We also address the effect of the ever present modulation broadening. Results of experiments in which sets of nine scans (direct absorption, 1f, 2f,??,8f; i.e., detection harmonic N=0,1,2,3,??,8) were made simultaneously are described and discussed. Finally, the role that increased structure plays??as a result of increasing order of detection, N, as well as from the modification of the signal profile with increasing optical thickness??is outlined from the perspective of classical information theory.     

Simultaneous CO concentration and temperature measurements using tunable diode laser absorption spectroscopy near 2.3 μm

Simultaneous measurements of carbon monoxide (CO) mole fraction and temperature using tunable diode laser absorption spectroscopy (TDLAS) near 2.3 μm are reported. The measurement method uses ro-vibrational transitions [R(27): v″ = 1 → v′ = 3] and [R(6): v″ = 0 → v′ = 2] in the first overtone band of CO near 2.3 μm (~4,278 cm^?1). The measurements were performed in the post flame environment of fuel rich premixed ethylene–air flames with a N₂ co-flow, stabilized over a water cooled McKenna burner. Non-uniformity in the temperature and CO mole fraction, along the absorption line of sight, in the mixing layer of the co-flow, was considered during data analysis. The TDLAS based temperature measurements (±80 K) were in good agreement with those obtained using N₂ vibrational coherent anti-Stokes Raman scattering (±20 K), and the CO mole fraction measurements were in good agreement with the equilibrium values, for equivalence ratios lower than 1.8. A signal to noise ratio of 45 was achieved at an equivalence ratio of 1 for a CO concentration of 0.8 % at 1,854 K.     

Background-free absorption spectroscopy using delayed balanced detection

A new, simple, background-free absorption spectroscopy technique is used to measure the absorption spectrum of acetylene from 1539.7 to 1542.4 nm at 10-kHz repetition rate. Whereas more traditional background-free methods such as wavelength-modulation spectroscopy (WMS) or frequency-modulation spectroscopy (FMS) rely on modulating the injection current of the light source as well as lock-in detection, this new approach directly yields a difference signal through delayed balanced detection that is equivalent to the 1f signal in WMS. Residual amplitude-modulation (RAM), which can be problematic in WMS and FMS, is not present in this method because no dithering of the injection current is required. In addition, virtually any modulation depth can be realized simply by adjusting an optical delay line.     

A mid-infrared scanned-wavelength laser absorption sensor for carbon monoxide and temperature measurements from 900 to 4000 K

Mid-infrared laser absorption sensors based on quantum cascade laser (QCL) technology offer the potential for high-sensitivity, selective, and high-speed measurements of temperature and concentration for species of interest in high-temperature environments, such as those found in combustion devices. A new mid-infrared QCL absorption sensor for carbon monoxide and temperature measurements has been developed near the intensity peak of the CO fundamental band at 4.6 μm, providing orders-of-magnitude greater sensitivity than the overtone bands accessible with telecommunications lasers. The sensor is capable of probing the R(9), R(10), R(17), and R(18) transitions of the CO fundamental ro-vibrational band which are located at frequencies where H₂O and CO₂ spectral interference is minimal. Temperature measurements are made via scanned-wavelength two-line ratio techniques using either the R(9) and R(17) or the R(10) and R(18) line pairs. The high-speed (1–2 kHz) scanned-wavelength sensor is demonstrated in room-temperature gas cell measurements of CO and, to demonstrate the potential of the sensor for high-temperature thermometry, in shock-heated gases containing CO for a very wide range of temperature (950–3500 K) near 1 atm. To our knowledge, these measurements represent the first use of QCL-based absorption sensor for thermometry at elevated combustion-like temperatures. The high-temperature measurements of CO mole fraction and temperature agree with the post-reflected-shock conditions within ±1.5% and ±1.2% (1σ deviation), respectively.     

Excitation of short-wave oscillations in the ionospheric plasma by the field of a high-power radio wave with extraordinary polarization due to induced scattering by ions

We analyze excitation of electron-cyclotron or upper hybrid oscillations of the ionospheric plasma at a frequency that is close to the pump frequency as a result of induced scattering of a high-power radio wave with extraordinary polarization by ions. The excited oscillations have a small wavelength of the order of the Larmor electron radius, which allows them to propagate near and below the reflection level of an extraordinary radio wave. We found the instability increment and threshold field, which results from collisional absorption of plasma waves. It is shown that the threshold field is minimal near the reflection level of an extraordinary radio wave when the radio wave frequency f₀ is between electron harmonics nf_Be with n≥2. In an ionospheric F layer it is of the order of 1 W/m. Such fields are easily obtained in ionospheric heating experiments allowing for radio-wave field swelling in the reflection region. In the vicinity of electron harmonics f_o≅nf_Be, the threshold field is increasing. For f_o<nf_Be with f_o≅nf_Be the instability does not develop because of the absence of plasma oscillations with a frequency that is close to the pump frequency (the latter also refers to the case f_o<2f_Be). The expressions obtained are generalized to the case in which the instability under consideration is excited by the field of an ordinary radio wave in the region of its quasilongitudinal propagation. We discuss the possibility of using the emergence of very short-wave plasma oscillations for explaining the experimentally observed phenomena. Institute of Terrestrial Magnetism, Ionosphere and Radio Wave Propagation, Russian Academy of Sciences, Troitsk, Moscow Region, Russia. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Radiofizika, Vol. 40, No. 5, pp. 541–560, May, 1997.     

CO concentration and temperature measurements in a shock tube for Martian mixtures by coupling OES and TDLAS

CO concentration and gas temperature distribution are diagnosed behind a strong shock wave simulating the Martian atmosphere entry processes by coupling optical emission spectroscopy (OES) and tunable diode laser absorption spectroscopy (TDLAS). The strong shock wave (6.31 ± 0.11 km/s) is established in a shock tube driven by combustion of hydrogen and oxygen. Temperature of the shock-heated gas is inferred through a precise analysis of the high temporal and spatial resolution experimental spectral of CN violet system (B ² Σ ⁺ →X ² Σ ⁺, Δv = 0 sequence) using OES. A CO absorption line near 2,335.778 nm is utilized for detecting the CO concentration using scanned-wavelength direct absorption mode with 50 kHz repetition rate. Combined with temperature results from OES, CO concentration in the thermal equilibrium region is derived. The current experimental results are complementary for determining an accurate rate coefficient of CO₂ dissociation and validation relevant chemical kinetics models in Mars atmosphere entry processes.     

Optical pathlength saturation signatures in wavelength modulation spectroscopy signals of atmospheric molecular oxygen

We discuss experimental and theoretical results of absorption features of the oxygen A-band transitions in the optically thick regime when synchronous detection at higher harmonics (N≥2), using wavelength modulation spectroscopy (WMS), is performed. We show that the absorption saturation effects demonstrate a distinctive feature which results in suppression of the line-center lobes of the harmonic signals. These effects depend on the optical pathlength as well as on the modulation index. The rich structure of WMS signals, especially at higher detection orders, is central to the technique’s advantages in resolving spectra congested with highly disparate oscillator-strength lines. The effect of pathlength saturation on this structure is investigated.     

Highly stable piezoelectrically tunable optical cavities

We have studied the effect on 2nd harmonic wavelength modulation spectroscopy of the use of integrating spheres as multipass gas cells. The gas lineshape becomes distorted at high concentrations, as a consequence of the exponential pathlength distribution of the sphere, introducing nonlinearity beyond that expected from the Beer–Lambert law. We have modelled this numerically for methane absorption at 1.651 μm, with gas concentrations in the range of 0–2.5 %vol in air. The results of this model compare well with experimental measurements. The nonlinearity for the 2fWMS measurements is larger than that for direct scan measurements; if this additional effect were not accounted for, the resulting error would be approximately 20 % of the reading at a concentration of 2.5 %vol methane.     

Single-QCL-based absorption sensor for simultaneous trace-gas detection of CH4 and N2O

A quantum cascade laser (QCL)-based absorption sensor for the simultaneous dual-species monitoring of CH₄ and N₂O was developed using a novel compact multipass gas cell (MGC). This sensor uses a thermoelectrically cooled, continuous wave, distributed feedback QCL operating at ~7.8 µm. The QCL wavelength was scanned over two neighboring CH₄ (1275.04 cm^?1) and N₂O (1274.61 cm^?1) lines at a 1 Hz repetition rate. Wavelength modulation spectroscopy (f = 10 kHz) with second harmonic (2f) detection was performed to enhance the signal-to-noise ratio. An ultra-compact MGC (16.9 cm long and a 225 ml sampling volume) was utilized to achieve an effective optical path length of 57.6 m. With such a sensor configuration, a detection limit of 5.9 ppb for CH₄ and 2.6 ppb for N₂O was achieved, respectively, at 1-s averaging time.     

Spectra of Stimulated Electromagnetic Emission of the Ionosphere Upon Sweeping of the Pump Wave Frequency Near Gyroharmonics. I. Experimental Results

We present the results of experimental studies of the spectra of the stimulated electromagnetic emission excited in the ionosphere by powerful radio waves during the pump wave frequency sweeping near the forth (n = 4) and fifth (n = 5) harmonics of the electron cyclotron frequency nf _ce. The frequency sweep was carried out for long (continuous) pumping in vertical and inclined directions (at 14° and 18° south of the zenith), as well as for the pulse diagnostic wave both with and without additional pumping far from the gyroharmonics. The dependences of the spectral features of the stimulated electromagnetic emission on the ratio between the pump-wave frequency f ₀ (or on the diagnostic-wave frequency f_DW) and nf _ce were analyzed. It is found that near the multiple gyroresonance, different spectral features of the stimulated emission are quenched at the same frequency for different pump-wave frequencies. For a sufficiently large inclination of the pump wave beam from the vertical direction, the intensity of the stimulated electromagnetic emission is notably decreased for f ₀ ≲ nf _ce as compared with f ₀ > nf _ce. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Radiofizika, Vol. 51, No. 6, pp. 461–476, June 2008.     

Intensity,transition moment,and bandshapes for the second overtone of compressed CO

Infrared spectra of the CO second overtone absorption band have been studied for pressures up to 156 bar. The absolute intensity, obtained from direct measurements of the total band, is found to be (1.27 ± 0.04) × 10^-2cm^-2Am^-1 at 298 K. Using the vibrational moments for the ground state and the transitions 0–1 to 0–4, we have evaluated the coefficients M₀ to M₄ of the quartic dipole moment function for CO and the coefficients of the vibration-rotation interaction functions. The normalized 0–3 band contours of compressed CO were first generated by summing the pressure-broadened rotational lines with Lorentz profiles. A discrepancy appears between calculated and observed bandshapes and increases with density. An empirical model, which involves the sum of CO self-broadened lines with profile described as the product of a Lorentz function by a fitted exponential function, gives reasonable agreement with the experiments. The interference effects resulting from overlapping lines have been estimated within the impact approximation.     

Absolute, spatially resolved, in situ CO profiles in atmospheric laminar counter-flow diffusion flames using 2.3?μm TDLAS

We developed a new, spatially traversing, direct tunable diode laser absorption spectrometer (TDLAS) for quantitative, calibration-free, and spatially resolved in situ measurements of CO profiles in atmospheric, laminar, non-premixed CH₄/air model flames stabilized at a Tsuji counter-flow burner. The spectrometer employed a carefully characterized, room temperature distributed feedback diode laser to detect the R20 line of CO near 2,313?nm (4,324.4?cm^?1), which allows to minimize spectral CH₄ interference and detect CO even in very fuel-rich zones of the flame. The burner head was traversed through the 0.5?mm diameter laser beam in order to derive spatially resolved CO profiles in the only 60-mm wide CH₄/air flame. Our multiple Voigt line Levenberg?CMarquardt fitting algorithm and the use of highly efficient optical disturbance correction algorithms for treating transmission and background emission fluctuations as well as careful fringe interference suppression permitted to achieve a fractional optical resolution of up to 2.4?×?10^?4 OD (1??) in the flame (T up to 1,965?K). Highly accurate, spatially resolved, absolute gas temperature profiles, needed to compute mole fraction and correct for spectroscopic temperature dependencies, were determined with a spatial resolution of 65???m using ro-vibrational N₂-CARS (Coherent anti-Stokes Raman spectroscopy). With this setup we achieved temperature-dependent CO detection limits at the R20 line of 250?C2,000?ppmv at peak CO concentrations of up to 4?vol.%. This permitted local CO detection with signal to noise ratios of more than 77. The CO TDLAS spectrometer was then used to determine absolute, spatially resolved in situ CO concentrations in the Tsuji flame, investigate the strain dependence of the CO Profiles and favorably compare the results to a new flame-chemistry model.     

Study of optical properties in a cubic quantum dot

In this paper, the effect of hydrostatic pressure on both the intersubband optical absorption coefficients and the refractive index changes is studied for typical GaAs/Al _x  Ga_1?x As cubic quantum dot. We use analytical expressions for the linear and third-order nonlinear intersubband absorption coefficients and refractive index changes obtained by the compact-density matrix formalism. The linear, third-order nonlinear, and total intersubband absorption coefficients and refractive index changes are calculated at different pressures as a function of the photon energy with known values of box length (L), the incident optical intensity (I), and Al concentration (x). According to the results obtained from the present work, we have found that the pressure plays an important role in the intersubband optical absorption coefficient and refractive index changes in a cubic quantum dot.     

In situ sensor for cycle-resolved measurement of temperature and mole fractions in IC engine exhaust gases

We present a multi-species mole fraction and temperature sensor for in situ exhaust gas diagnostic of internal combustion (IC) engines. The sensor is based on Tunable Diode Laser Absorption Spectroscopy (TDLAS) and incorporates four optical channels - two miniature White cells and two double-traversal cells - with base lengths of 6?cm. It has been demonstrated at a hot air test stand and in the exhaust manifold of a single-cylinder research engine, with measured temperatures of up to 1000?K. Stable operation was achieved with absorption lengths of up to 192?cm (test stand) and 97?cm (engine). Employing time-division multiplexed detection, six species were measured simultaneously in the engine exhaust, at wavelengths ranging from 1.4?µm to 5.2 µm: water vapor (H₂O), carbon dioxide (CO₂), carbon monoxide (CO), methane (CH₄), nitrogen dioxide (NO₂) and nitric oxide (NO). The effective measurement rate was as high as 1?kHz, and cycle-to-cycle variations were clearly detected. We show the correlation of the air-fuel equivalence ratio with the spectroscopically measured mole fraction of each species. At a cycle-resolved rate, detection limits for the legally regulated species NO and NO₂ were 1?ppm and 4?ppm, respectively. The sensor is intended to help improve the understanding of IC engine emission behavior during fast transients.     

Wavelength modulation absorption spectrometry from optically saturated collision-broadened transitions

A theoretical investigation of the influence of optical saturation on wavelength modulation absorption spectrometry (WMAS) signals from collision-broadened transitions is presented. Expressions are derived for the nth Fourier coefficient of the analytical detector signal, and thereby also for the nth harmonic signal from a WMAS instrumentation (i.e. the nf-WMAS signal), from a wavelength modulated collision-broadened transition exposed to optical saturation. The flux- (or irradiance-) and modulation-amplitude dependences of the nf-WMAS signal on resonance are scrutinized in detail. It is shown that the nth Fourier coefficient of the wavelength modulated analytical detector signal from an optically saturated collision-broadened transition can be written as a product of a flux-dependent (φ) bleaching function, given by (1+φ/φ_sat)^-1 and identical to that appearing for ordinary, unmodulated absorption spectrometry (AS), and a flux-, detuning-, and modulation-amplitude-dependent wavelength modulated peak-normalized saturation-broadened Lorentzian lineshape function, specific for the WMAS technique. It is found that the nf-WMAS signal on resonance decreases faster than an ordinary AS signal as a function of laser flux when smaller-than-optimum modulation amplitudes are used, but slower when larger-than-optimum modulation amplitudes are used. When optimum (or close-to-optimum) modulation amplitudes are being used, on the other hand, the flux dependence of the WMAS signal resembles to a large degree that of ordinary AS. The conditions for when WMAS from collision-broadened transitions has the same flux dependence as ordinary AS are identified.