Diode laser absorption measurements of CH(3)Cl and CH(4) near 1.65 microm

Two distributed-feedback (InGaAsP) diode lasers were used to record high-resolution absorption spectra of the parallel and the perpendicular components of the 2nu(4) band of methyl chloride (CH(3)Cl) and the 2nu(3) band of methane (CH(4)) near 1.65 mum. The room-temperature absorption measurements, which were conducted in a multipass cell with a variable path length (878-1020 cm), were used to determine the mole fractions of the constituent gases and thus demonstrate species-specific, nonintrusive concentration measurements of species with overlapping spectra.     

Intracavity CO laser photoacoustic trace gas detection: cyclic CH(4), H(2)O and CO(2) emission by cockroaches and scarab beetles

A liquid-nitrogen-cooled CO laser and an intracavity resonant photoacoustic cell are employed to monitor trace gases. The setup was designed to monitor trace gas emissions of biological samples on line. The arrangement offers the possibility to measure gases at the 10(9) by volume (ppbv) level (e.g., CH(4), H(2) O) and to detect rapid changes in trace gas emission. A detection limit of 1 ppbv for CH(4) in N(2) equivalent to a minimal detectable absorption of 3 × 10(-9) cm(-1) can be achieved. Because of the kinetic cooling effect we lowered the detection limit for CH(4) in air is decreased to 10 ppbv. We used the instrument in a first application to measure the CH(4) and H(2) O emission of individual cockroaches and scarab beetles. These emissions could be correlated with CO(2) emissions that were recorded simultaneously with an infrared gas analyzer. Characteristic breathing patterns of the insects could be observed; unexpectedly methane was also found to be released.     

Airborne laser infrared absorption spectrometer (ALIAS-II) for in situ atmospheric measurements of N2O, CH4, CO, HCl, and NO2 from balloon or remotely piloted aircraft platforms

The Airborne Laser Infrared Absorption Spectrometer II (ALIAS-II) is a lightweight, high-resolution (0.0003-cm(-1)), scanning, mid-infrared absorption spectrometer based on cooled (80 K) lead-salt tunable diode laser sources. It is designed to make in situ measurements in the lower and middle stratosphere on either a balloon platform or high-altitude remotely piloted aircraft. Chemical species that can be measured precisely include long-lived tracers N(2)O and CH(4), the shorter-lived tracer CO, and chemically active species HCl and NO(2). Advances in electronic instrumentation developed for ALIAS-I, with the experience of more than 250 flights on board NASA's ER-2 aircraft, have been implemented in ALIAS-II. The two-channel spectrometer features an open cradle, multipass absorption cell to ensure minimal contamination from inlet and surfaces. Time resolution of the instrument is 相似文献   

Isochoric (p,v, T) measurements on CO2 and (0.98 CO2+0.02 CH4) from 225 to 400 K and pressures to 35 MPa

Comprehensive isochoric (p, v, T) measurements have been obtained for (0.98 CO₂+0.02 CH₄) at densities from 1 to 26mol·dm^–3. Supplemental isochoric (p, v, T) measurements have been obtained for high-purity CO₂ at densities from 12 to 24 mol·dm^–3. Measurements of p(T) cover a broad range of temperature, 225 to 400 K, at pressures to 35 MPa. Comparisons have been made with independent sources and with a predictive method based on corresponding states.     

Quantitative measurements of CO2 and CH4 using a multipass Raman capillary cell

Raman measurements of two common gases are made using a simple multipass capillary Raman cell (MCC) coupled to an unfiltered 18 around 1 fiber-optic Raman probe. The MCC, which is fabricated by chemical deposition of silver on the inner walls of a 2 mm inner diameter glass capillary tube, gives up to 20-fold signal enhancements for nonabsorbing gases. The device is relatively small and suitable for remote and in situ Raman measurements with optical fibers. The optical behavior of the MCC is similar to previously described liquid-core waveguides and hollow metal-coated waveguides used for laser transmission, but unlike the former devices, the MCC is generally applicable to a very wide range of nonabsorbing gases.     

High-precision direct measurements of (13)CH(4)/(12)CH(4) and (12)CH(3)D/(12)CH(4) ratios in atmospheric methane sources by means of a long-path tunable diode laser absorption spectrometer

Measurements of (13)CH(4)/(12)CH(4) and (12)CH(3)D/(12)CH(4) ratios in atmospheric methane (CH(4)) sources provide important information about the global CH(4) budget as well as about CH(4) production and consumption processes occurring within the various sources. As an alternative to the conventional mass spectrometer (MS) technique, which requires conversion of CH(4) to CO(2) and H(2), we have developed a tunable diode laser absorption spectrometer (TDLAS), which permits rapid direct measurements of the (13)CH(4)/(12)CH(4) and (12)CH(3)D/(12)CH(4) ratios. An intercomparison between TDLAS and MS techniques for samples from natural wetlands, landfills, and natural gas sources resulted in a mean deviation of Δδ(13)C = 0.44‰ and ΔδD = 5.1‰. In the present system the minimum mixing ratios required are 50 parts in 10(6) by volume (ppmv) CH(4) (sample size 2 μmol CH(4)) for direct δ(13)C measurements and 2000 ppmv (sample size 80 μmol CH(4)) for direct δD measurements. These mixing-ratio limits are adequate for most CH(4) source characterization studies without requiring sample preconcentration.     

Satellite vibration measurements with an autodyne CO(2) laser radar

Vibration signatures of the Low Power Atmospheric Compensation Experiment satellite were obtained with a ground-based CO(2) laser radar. The laser radar operated in a cw mode and used autodyne receivers to extract relative target velocity information between a germanium retroreflector located at the base of the satellite and a retroreflector array located at the tip of an extended forward boom. Time-frequency analysis algorithms were applied to the vibration data to investigate the correlation between excitations and modal structure. The resultant analysis suggests that vibration modes of an on-orbit spacecraft can be suppressed with simple open-loop techniques.     

Solid-state reaction synthesized Pd-doped tin oxide thick film sensor for detection of H2, CO, LPG and CH4

This paper deals with the synthesis of tin oxide (SnO₂) nano-powders by a solid-state reaction technique. The synthesized powders have been characterized by simultaneous thermo gravimetric and differential thermal analysis (TG–DTA) and X-ray diffraction (XRD) techniques. Suitable calcination temperature is established by XRD and TG–DTA analysis. Thick film sensors have been developed from as-prepared undoped and palladium (Pd) doped (0.5 and 1 wt%) SnO₂ powders using screen printing technology for the detection of various pollutant gases such as, hydrogen (H₂), carbon monoxide (CO), liquefied petroleum gas (LPG) and methane (CH₄). The surface of the thick film sensor has been characterized by field emission scanning electron microscopy (FESEM). The sensing characteristics of thick films have been studied from the aspect of crystallite size of sensing material and microstructure of the thick film surface. It is found that SnO₂ doped with 1 % Pd exhibits the maximum sensitivity (79 %) towards CO gas along with fast response/recovery time (80 s, 197 s) and almost insensitive for H₂, LPG and CH₄.     

Polymeric amine membrane materials for carbon dioxide (CO2)/methane (CH4) separation

Carbon dioxide separation from methane using membrane technology is getting attraction, and polymeric membranes are the most prominent polymer membrane materials. However, the existing polymeric membranes performance is inadequate due to trade-off limitation open new windows to explore. Therefore, in this study, amine polymeric membrane (APM) has been fabricated by the addition of different concentration (5 wt.% and 15 wt.%) of diethanolamine (DEA). The developed amine polymeric membranes have been characterized in term of morphology and thermal analysis using field emission scanning electron microscope and thermogravimetric analyzer, respectively. The permeance and selectivity have been determined by using pure carbon dioxide (CO₂) and methane (CH₄). Also, the effect of amine concentration on permeance and selectivity has been studied. The results confirmed the symmetric and homogenous structure and thermal stability of membranes up to 490 °C. The maximum percent increase by the 15 wt.% addition of diethanolamine is 102.08 % at 10 bar pressure.     

气体中微量一氧化碳、甲烷、二氧化碳的气相色谱分析

建立了甲烷转化气相色谱法测定气体中一氧化碳、甲烷、二氧化碳的分析方法。采用一阀两柱系统,氯气、氯化氢通过十通阀经柱Ⅰ(Hayesep Q)反吹出系统,一氧化碳、甲烷、二氧化碳通过柱Ⅱ(Porapak Q)进入氢火焰离子化检测器进行检测,通过外标法定量,结果表明该方法线性好,各组分的检出限分别为一氧化碳0.02×10-6(mol/mol)、甲烷0.05×10-6(mol/mol)、二氧化碳0.08×10-6(mol/mol)。该方法简便、准确、灵敏、重现好。     

In situ combustion measurements of CO, H2O, and temperature with a 1.58-microm diode laser and two-tone frequency modulation

An optical near-infrared process sensor for electric arc furnace pollution control and energy efficiency is proposed. A near-IR tunable diode laser has performed simultaneous in situ measurements of CO (1577.96 nm), H(2)O (1577.8 and 1578.1 nm), and temperature in the exhaust gas region above a laboratory burner fueled with methane and propane. The applicable range of conditions tested is representative of those found in a commercial electric arc furnace and includes temperatures from 1250 to 1750 K, CO concentrations from 0 to 10%, and H(2)O concentrations from 3 to 27%. Two-tone frequency modulation was used to increase the detection sensitivity. An analysis of the method's accuracy has been conducted with 209 calibration and 105 unique test burner setpoints. Based on the standard deviation of differences between optical predictions and independently measured values, the minimum accuracy of the technique has been estimated as 36 K for temperature, 0.5% for CO, and 3% for H(2)O for all 105 test data points. This accuracy is sufficient for electric arc furnace control. The sensor's ability to nonintrusively measure CO and temperature in real time will allow for improved process control in this application.     

Single diode laser sensor for wide-range H2O temperature measurements

A single diode laser absorption sensor (near 1477 nm) useful for simultaneous temperature and H2O concentration measurements is developed. The diode laser tunes approximately 1.2 cm(-1) over three H2O absorption transitions in each measurement. The line strengths of the transitions are measured over a temperature range from 468 to 977 K, based on high-resolution absorption measurements in a heated static cell. The results indicate that the selected transitions are suitable for sensitive temperature measurements in atmospheric pressure combustion systems using absorption line ratios. Comparing the results with HITRAN 96 data, it appears that these transitions will be sensitive over a wide range of temperatures (450-2000 K), suggesting applicability for combustion measurements.     

Vapour-liquid equilibrium of the CH4Ar,CH4CO,and ARCO systems at elevated pressures

High pressure vapour-liquid equilibrium data for the CH₄Ar, CH₄CO, and ArCO systems are presented in this work. The data are obtained isothermally and for each data point T, P, x_i, and y_i are measured. When possible, the measurements are compared to other published data, and good agreement is found with previous investigations.Each isotherm is subjected to a thermodynamic analysis, and activity coefficients are calculated. When both components are condensable, the ordinary symmetrical convention for normalization of activity coefficients is used, and when one component is supercritical, the unsymmetrical convention is used.The activity coefficients are adjusted to a constant pressure via the Poynting correction factor, and these pressure adjusted activity coefficients are subjected to a thermodynamic consistency test based on the isothermal-isobasic form of the Gibbs-Duhem equation. It is found that the maximum inconsistency for the data presented in this work is 10%.     

CO_2/CH_4分离膜技术在沼气提纯中的应用研究进展

生物天然气(BNG)是近年来新兴的一种可再生清洁能源.制备生物天然气的核心是去除沼气中的二氧化碳.CO2/CH4分离膜技术被认为是未来沼气提纯领域最有潜力的一项技术.本文对CO2/CH4分离膜技术在沼气提纯中的应用研究和发展现状进行综述,包括CO2/CH4分离膜材料的最新发展;膜法沼气提纯工艺过程的设计;欧美膜法沼气提纯工业化装置的近况等;最后对膜法沼气提纯技术的主要困难及未来发展方向进行分析与讨论.     

Lightweight diode laser spectrometer CHILD (Compact High-altitude iN-situ Laser Diode) for balloonborne measurements of water vapor and methane

A new lightweight near-infrared tunable diode laser spectrometer CHILD (Compact High-altitude In-situ Laser Diode spectrometer) was developed for flights to the stratosphere as an additional in situ sensor on existing balloonborne payloads. Free-air absorption measurements in the near infrared are made with an open-path Herriott cell with new design features. It offers two individual absorption path lengths optimized for CH4 with 74 m (136 pass) and H2O with 36 m (66 pass). New electronic features include a real-time gain control loop that provides an autocalibration function. In flight-ready configuration the instrument mass is approximately 20 kg, including batteries. It successfully measured stratospheric CH4 and H2O profiles on high-altitude balloons on four balloon campaigns (Environmental Satellite validation) between October 2001 and June 2003. On these first flights, in situ spectra were recorded from ground level to 32,000-m altitude with a sensitivity of 0.1 ppm [(parts per million), ground] to 0.4 ppm (32,000 m) for methane and 0.15-0.5 ppm for water.     

Highly Active,Durable Ultrathin MoTe2 Layers for the Electroreduction of CO2 to CH4

The electroreduction of CO₂ to CH₄ is a highly desirable, challenging research topic. In this study, an electrocatalytic system comprising ultrathin MoTe₂ layers and an ionic liquid electrolyte for the reduction of CO₂ to methane is reported, efficiently affording methane with a faradaic efficiency of 83 ± 3% (similar to the best Cu‐based catalysts reported thus far) and a durable activity of greater than 45 h at a relatively high current density of 25.6 mA cm^?2 (?1.0 V_RHE). The results obtained can facilitate research on the design of other transition‐metal dichalcogenide electrocatalysts for the reduction of CO₂ to valuable fuels.     

Photocatalytic transformation of CO2 to CH4 and CO on acidic surface of TiO2 anatase

Recently, many studies have demonstrated that carbon dioxide can be converted to methane on TiO₂ surface by a photocatalytic process. We show that such a photo-reduction can be significantly affected by the presence of an acidic proton in powder samples of titania. Using in situ absorption gas-phase rovibrational spectroscopic detection of CH₄, CO and CO₂, we demonstrate that proton enhancement positively affects transformation of intermediate derivatives to methane during the photo-irradiation process via several reactions in which the electron transfer inside titania is coupled to oxygen transfer to the Ti³⁺ centers of TiO₂ structure. The yield of CH₄ or CO depends on the surface conditioning of titania: the formation of CH₄ is boosted by a presence of adsorbed HCl, while the formation of CO is boosted by adsorbed H₂SO₄.     

Near-infrared combination and overtone bands of the CH2 sequence in CH2X2, CH2XCHX2, and CH3(CH2)5CH3 and their characteristic frequency zones

We characterized near-infrared spectra of the CH2 sequence in CH2X2 (X=halogen), CH2ClCHCl2, and CH3(CH2)5CH3. Each near-infrared absorption in the region from 3500 to 10,000 cm-1 is consistently assigned to one of the five different combination or overtone groups, in the order of increasing frequency, of the {[v(CH)]+[delta(CH)]} (A), {[v(CH)]+[2delta(CH)]} (B), [2v(CH)] (C), {[2v(CH)]+[delta(CH)]} (D), and [3v(CH)] (E) types, where v(CH) and delta(CH) denote the CH stretching and CH deformation normal modes, respectively. Each group has its own characteristic frequency zone. The bands of B, D, and E, which are second-order combinations or overtones, are weaker by 1/10-1/50 than those of A and C, which are first-order combinations or overtones. The near-infrared spectra of the CH2 sequence show "window zones" of very weak or no absorptions. This suggests that we can perceive the characteristic near-infrared bands of a functional group through the window zones, and we give an example to demonstrate this. The first-order combination bands of type A only of CH2X2 are reasonably assigned to a pair of the normal modes of v(CH) and delta(CH). From this we predict that the first-order combination bands should give structural information on the CH2 chain, similar to the infrared fundamental bands.