采用PTV技术研究循环流化床内气固两相流动

采用PTV技术对循环流化床顶部颗粒稀疏流动区域进行了测量，其中采用先进的高速摄像技术获取流动的连续图像，并采用目前有望在气固两相流动测量中发挥较大作用的四种PTV算法：BICC法、VGT法、SPRING法和4-FRAME法，对所获取的图像进行颗粒配对处理，从而得到流场中运动颗粒的速度信息。所得到的结论为：本文所采用的PTV算法在图像处理中都产生少量的伪矢量，通过采取简单的伪矢量识别算法就可以剔除大部分伪矢量；本文实验条件下，测得循环流化床顶部区域内颗粒运动速度差别较小。本文工作为进一步详细实验测量研究奠定了理论与技术基础。     

Simultaneous measurement of size and velocity of microbubbles moving in an opaque tube using an X-ray particle tracking velocimetry technique

An X-ray particle tracking velocimetry (PTV) technique was developed to simultaneously measure the sizes and velocities of microbubbles in a fluid without optical aberration. This technique is based on a combination of in-line X-ray holography and PTV. The X-ray PTV technique uses a configuration similar to that of conventional optical imaging techniques, and is easy to implement. In the present work, microbubbles generated from a fine wire by electrical heating were used as tracer particles. The X-ray PTV technique simultaneously recorded size and velocity data for microbubbles (_b=10–60 m) moving upward in an opaque tube (inner diameter =2.7 mm). Due to the different refractive indices of water and air, phase contrast X-ray images clearly show the exact size and shape of overlapped microbubbles. In all of the working fluids tested (deionised water and 0.01 M and 0.10 M NaCl solutions), the measured terminal velocity of the microbubbles rising through the solution was proportional to the square of the bubble diameter. The proposed technique can be used to extract useful information on the behaviour of various bio/microscale fluid flows that are not amenable to analysis using conventional methods.     

Development of split–splitless PTV large-volume injection for analytes covering a wide boiling point range

A programmed-temperature vaporiser (PTV)–large-volume injection (LVI) method with a two-stage evaporation process was developed capable of effectively introducing analytes covering a wide boiling-point range (from that of n-nonane to that of n-tetracontane). The method uses speed-controlled sample introduction (50 µL) and a simple PTV setup with Peltier Cooling. Besides, an important cause of discrimination of high-boiling compounds in LVI was identified. The method was successfully applied to simplify the sample preparation in the extractable petroleum hydrocarbon analysis of water and soil samples. The method proved to be resistant to matrix contamination. Linearity was tested between 0.01 and 20 µg mL^?1. The correlation coefficients ranged from 0.996 to 0.999. The relative standard deviation calculated from five parallel runs was 2.73%. The major advantage of the method is its simplicity making it an attainable choice for smaller environmental laboratories.     

程序升温大体积进样和解卷积气相色谱-质谱法测定蔬菜水果中32种农药残留量

建立了蔬菜、水果中有机磷、有机氯、拟除虫菊酯和氨基甲酸酯等32种农药的气相色谱-质谱(GC-MS)检测方法。样品经乙腈提取,石墨碳黑串联丙氨基固相萃取柱净化,采用程序升温大体积进样,GC-MS全扫描模式采集,结合解卷积技术定性分析,内标法定量。分别对程序升温和大体积进样等条件进行了研究,并考察了方法选择性和耐用性。在最优条件下,32种农药的响应值与浓度呈良好的线性关系(r>0.995),各农药的方法检出限为2.0~5.0 μg/kg,以菠菜、四季豆和黄瓜为代表基质,进行3个水平(0.010~0.50 mg/kg)的加标回收试验(n=6),回收率为65.2%~120.3%,相对标准偏差(RSD)为4.1%~22.3%。该方法快速、灵敏、可靠、耐用,能满足蔬菜、水果中多类多残留痕量分析的要求。     

Flame/flow dynamics at the piston surface of an IC engine measured by high-speed PLIF and PTV

Resolving fluid transport at engine surfaces is required to predict transient heat loss, which is becoming increasingly important for the development of high-efficiency internal combustion engines (ICE). The limited number of available investigations have focused on non-reacting flows near engine surfaces, while this work focuses on the near-wall flow-field dynamics in response to a propagating flame front. Flow-field and flame distributions were measured simultaneously at kHz repetition rates using particle tracking velocimetry (PTV) and planar laser induced fluorescence (PLIF) of sulfur dioxide (SO₂). Measurements were performed near the piston surface of an optically accessible engine operating at 800?rpm with homogeneous, stoichiometric isooctane-air mixtures. High-speed measurements reveal a strong interdependency between near-wall flow and flame development which also influences subsequent combustion. A conditional analysis is performed to analyze flame/flow dynamics at the piston surface for cycles with ‘weak’ and ‘strong’ flow velocities parallel to the surface. Faster flame propagation associated with higher velocities before ignition demonstrates a stronger flow acceleration ahead of the flame. Flow acceleration associated with an advancing flame front is a transient feature that strongly influences boundary layer development. The distance from the wall to 75% maximum velocity (δ₇₅) is analyzed to compare boundary layer development between fired and motored datasets. Decreases in δ₇₅ are strongly related to flow acceleration produced by an approaching flame front. Measurements reveal strong deviations of the boundary layer flow between fired and motored datasets, emphasizing the need to consider transient flow behavior when modeling boundary layer physics for reacting flows.     

Programmed-Temperature Vaporizing (PTV) Liners to Introduce Chlorinated and Sulfur Compounds into a Capillary Gas Chromatograph

Introduction of a sample at a programmed temperature is an attractive approach both for dilute samples in large volumes and to prevent discrimination inside the syringe needle with this injection into a capillary gas Chromatograph. Quantitative data obtained with glass liners packed with trapping materials including glass wool, Tenax TA, Chromosorb 101 and Thermotrap-TA to analyze chlorinated and sulfur compounds are compared. To eliminate the solvent, these vapors were vented through the injection port cap, which provided greater efficiency than through the split line.     

Quantitation in capillary gas chromatography with emphasis on the problems of sample introduction

Sampling techniques for practical quantitative capillary GC have to meet certain principal requirements. Both the absolute and the relative peak areas (e.g. column loads) must be reproducible with high precision and at high accuracy; discrimination of certain constituents according to their volatility should not take place on sampling. On the basis of systematic studies, the three most reliable sampling techniques used for GC analyses with the aim of achieving precise and accurate quantitative data proved to be the following: On-column, injection, splitless PTV injection, and an optimized version of split sampling called “cooled needle split” injection. The on-column technique can be optimized by using precolumns with wider internal diameters and without stationary phase coatings to overcome the problems of large liquid sampling volumes and for automation. The PTV technique should only be used in the splitless mode because discrimination cannot be suppressed completely with the split mode. All three of the techniques can be operated automatically, either to avoid “human interference”, i.e. to improve precision or for unattended operation to save man-power.     

Splitless injection–development and state of the art. Including a comparison of matrix (“dirt”) effects in conventional and PTV splitless injection

Kurt Grob introduced splitless injection in 1969. He elaborated most of the working guidelines including the techniques required for reconcentrating the broad intial bands, i.e. the solvent effects and cold trapping. He also designed a vaporizing injector suited for splitless injection. Nevertheless, splitless injection is still often carried out using inappropriate conditions, and many of today's vaporizing injectors are not suited for splitless injection. No autosampler is available that introduces the sample at the appropriate position. Conventional splitless injection is compared to PTV splitless injection for the range of samples that cannot be handled by the anyway superior oncolumn injection, i.e. sample with high loads of involatile byproducts. There is a clear preference for PTV splitless injection as matrix effects observed in conventional splitless injection were found to be substantially reduced or even eliminated.     

Ultrasound-assisted extraction and on-line LC–GC–MS for determination of polycyclic aromatic hydrocarbons (PAH) in urban dust and diesel particulate matter

A method has been developed for determination of polycyclic aromatic hydrocarbons (PAH) in particulate matter from ambient air and diesel exhaust emissions. It is reproducible and accurate and, compared with similar methods for analysis of individual PAH components in complex matrices, it is relatively fast and simple. Single PAH components can be determined in samples of particulate matter from ambient air and diesel exhaust emissions with LOD of approximately 1 pg/sample. Further, sample throughput is high, because more than 20 samples can be extracted and prepared for analysis in one working (8-h) day. The particulate matter is subjected to ultrasound-assisted extraction, a technique that is shown to extract PAH from particulate material with efficiencies fully comparable with those of Soxhlet extraction. An aliphatic/PAH-enriched fraction is obtained by solid-phase extraction before isolation, separation, and identification/quantification of PAH by on-line liquid chromatography–gas chromatography–mass spectrometry. The method was validated by analysis of US National Institute of Standards and Technology (NIST) Standard Reference Materials (SRM) 1649a, Urban Dust, and 2975, Diesel Particulate Matter. Results from the method are in good agreement with the NIST-certified PAH concentrations and with NIST reference PAH concentrations.     

Use of open-tubular trapping columns for on-line extraction–capillary gas chromatography of aqueous samples

The applicability of open-tubular trapping columns for on-line extraction–capillary GC analysis is evaluated. The extraction step involves sorption of the analytes from water into the stationary phase of an open-tubular column, removal of the water by purging the trap with nitrogen, and desorption of the analytes with an organic solvent. The effect of swelling of the stationary phase with organic solvents on the retention power of the trap is studied. When using pentane or hexane as swelling agent breakthrough volumes of at least 10 ml can easily be obtained for non-polar compounds. For a number of medium polarity compounds breakthrough volumes of 5 ml can be achieved when chloroform is used as the swelling agent. The required drying time is less than 1 minute. Quantitative desorption requires only 75 μl of organic solvent. Solvent elimination prior to transfer to the GC column is carried out using a PTV injector and a multidimensional GC system. The system is applied for the analyses of river water, urine, and serum samples.