The study of electron beam flue gas treatment for coal-fired thermal plant in Japan

The fundamental research work with simulated coal-fired flue gas was performed in JAERI to get basic data for electron beam treatment of flue gas from thermal power plants in Japan. The standard condition of the experiments was set to be the same as that of next large scale pilot test in Nagoya. The concentrations of NO_x and SO_x were 225 ppm and 800 ppm, respectively. The temperature of the system was 65°C. The effect of multiple irradiation was observed for NO_x removal. The target SO_x and NO_x removals (94% and 80%, respectively) with low NH₃ leakage (less than 10 ppm) were achieved at 9 kGy irradiation with 0.9 NH₃ stoichiometry during 7 hours continuous operation. The facility for the pilot plant (12,000 Nm³/hr) has just built at the site of Shin-Nagoya power plant of Chubu Electric Power Company and will be started in full operation in November 1992.     

Pilot plant for flue gas treatment with electron beam -start up and two stage irradiation tests

The pilot plant for flue gas treatment with electron beam has been built at Power Plant Kaweczyn, near Warsaw. The irradiation part of the pilot plant has been put in operation in 1991 whereas the complete installation including bag filter started to work in spring 1992. The starting tests consisted of studying the components reliability and influence of the two-stage irradiation process on efficiency of NO_x removal. The results have shown that the two- stage irradiation leads to remarkable energy savings and retains high NO_x removal. The mathematical models of the double and triple irradiation process are discussed.     

Computer monitoring and control system (CMCS) for electron beam flue gas treatment

The computer monitoring and control system (VME based) with various facilities are described. The solution of preparing sampling probes and automatic calibration system is also presented.     

Kinetics of SO2 removal from flue gas by electron beam technique

Laboratory scale experiments were carried out in order to get more information about the oxidation of SO₂ by OH radicals (homogeneous reaction) and the oxidation of SO₂ at aerosol surfaces (heterogeneous reaction). For the experiment of homogeneous reaction, SO₂ was added to synthetic flue gas without initial NO and without ammonia and the mixture was irradiated with electron beam. The SO₂ removal was measured as a function of temperature and water vapour concentration at constant dose. For the experiment of heterogeneous reaction, SO₂ was added to nucleating sulfuric acid aerosol. No SO₂ removal was observed in this case. So, it can be concluded that the heterogeneous oxidation of SO₂ is negligible in the absence of ammonia. Therefore, the oxidation of SO₂ must be interpreted merely by homogeneous gas phase chemistry. The gas phase kinetics are derived from comparison of experimental results and computer modelling.     

Glow discharge electron impact ionization source for miniature mass spectrometers

A glow discharge electron impact ionization (GDEI) source was developed for operation using air as the support gas. An alternative to the use of thermoemission from a resistively heated filament electron source for miniature mass spectrometers, the GDEI source is shown to have advantages of long lifetime under high-pressure operation and low power consumption. The GDEI source was characterized using our laboratory's handheld mass spectrometer, the Mini 10. The effects of the discharge voltage and pressure were investigated. Design considerations are illustrated with calculations. Performance is demonstrated in a set of experimental tests. The results show that the low power requirements, mechanical ruggedness, and quality of the data produced using the small glow discharge ion source make it well-suited for use with a portable handheld mass spectrometer.     

Conversion of natural gas to C_2 hydrocarbons through dielectric-barrier discharge plasma catalysis

The experiments are carried out in the system of continuous flow reactors with dielectric-barrier discharge (DBD) for studies on the conversion of natural gas to C2 hydrocarbons through plasma catalysis under the atmosphere pressure and room temperature. The influence of discharge frequency, structure of electrode, discharge voltage, number of electrode, ratio of H2/CH4, flow rate and catalyst on conversion of methane and selectivity of C2 hydrocarbons are investigated. At the same time, the reaction process is investigated. Higher conversion of methane and selectivity of C2 hydrocarbons are achieved and deposited carbons are eliminated by proper choice of parameters. The appropriate operation parameters in dielectric-barrier discharge plasma field are that the supply voltage is 20-40 kV (8.4-40 W), the frequency of power supply is 20 kHz, the structure of (b) electrode is suitable, and the flow of methane is 20-60 ml · min-1. The conversion of methane can reach 45%, the selectivity of C2 hydrocarbons i     

High-throughput model-building and screening of zeolitic imidazolate frameworks for CO2 capture from flue gas

To find potential zeolitic imidazolate frameworks(ZIFs)for CO2 capture from flue gas,we built 169,898 ZIF models from 84,949 hypothetical zeolite networks.By calculating their lattice energies,accessible volumes to CO2,the isosteric adsorption heat(Qst)of H2 O,Henry’s constant ratio(SKH)of CO2/N2,percent regenerability(R%),CO2 working capacity(ΔNCO2),CO2/N2 adsorption selectivity(SCO2/N2))and adsorbent performance score(APS),we identi fied 49 hydrophobic ZIF structures that might outplay already-realised ZIFs built from the same imidazolate linkers for CO2 capture from flue gas.     

Validation of methods for measuring polychlorinated dibenzo- p -dioxins and furans,and dioxin-like polychlorinated biphenyls in flue gas

Method validation was performed on the collection and extraction procedures for an analysis of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (DLPCBs) in flue gas. The adoption of the rapid pressurized liquid extraction (PLE) technique was evaluated for extraction from polyurethane foam plugs (PUFPs) and fly ash. With respect to extraction from PUFPs, dichloromethane PLE showed an extraction efficiency equivalent to that of conventional acetone Soxhlet, while toluene PLE was found to have a lower extraction efficiency from fly ash than toluene Soxhlet. The collection ability of three sampling methods, employed in the Japanese standard analytical method JIS K0311 (revised in 2005) was evaluated by evaluating the distribution of gaseous PCDD/Fs and DLPCBs in each collection compartment in sampling trains. A DiOANA® fibrous alumina filter and a PUFP, newly employed trapping devices in the revised JIS method, were found to trap gaseous analytes effectively. The validation of the two newly employed sampling methods (DiOANA and PUFP) was tested by parallel measurements of the methods with a conventional five-impinger method, and good agreements on the PCDD/Fs and DLPCBs quantities were demonstrated.     

Contribution of UV light to the decomposition of toluene in dielectric barrier discharge plasma/photocatalysis system

The contribution of UV light from plasma and an external UV lamp to the decomposition of toluene in a dielectric barrier discharge (DBD) plasma/UV system, as well as in a plasma/photocatalysis system was investigated. It was found that UV light from the DBD reactor was very weak. Its contribution to the removal of toluene in the plasma/photocatalysis system could be ignored. Whereas, the introduction of external UV light to the plasma significantly improves the removal efficiency of toluene by 20%. The removal efficiency of toluene in the plasma/photocatalysis system increased about 22% and 16% when compared with a plasma only system and plasma driven photocatalyst system, respectively. The increased toluene removal efficiency was mostly attributed to the contribution of the synergy between plasma and UV light, but not to the synergy between plasma and photocatalysis. The synergetic effect between plasma and photocatalysis was not significant.     

Conversion of natural gas to C2 hydrocarbons through dielectric-barrier discharge plasma catalysis

The experiments are carried out in the system of continuous flow reactors with dielectric-barrier discharge (DBD) for studies on the conversion of natural gas to C₂ hydrocarbons through plasma catalysis under the atmosphere pressure and room temperature. The influence of discharge frequency, structure of electrode, discharge voltage, number of electrode, ratio of H₂/CH₄, flow rate and catalyst on conversion of methane and selectivity of C₂ hydrocarbons are investigated. At the same time, the reaction process is investigated. Higher conversion of methane and selectivity of C₂ hydrocarbons are achieved and deposited carbons are eliminated by proper choice of parameters. The appropriate operation parameters in dielectric-barrier discharge plasma field are that the supply voltage is 20–40 kV (8.4–40 W), the frequency of power supply is 20 kHz, the structure of (b) electrode is suitable, and the flow of methane is 20–60 mL · min⁻¹. The conversion of methane can reach 45%, the selectivity of C₂ hydrocarbons is 76%, and the total selectivity of C₂ hydrocarbons and C₃ hydrocarbons is nearly 100%. The conversion of methane increases with the increase of voltage and decreases with the flow of methane increase; the selectivity of C₂ hydrocarbons decreases with the increase of voltage and increases with the flow of methane increase. The selectivity of C₂ hydrocarbons is improved with catalyst for conversion of natural gas to C₂ hydrocarbons in plasma field. Methane molecule collision with radicals is mainly responsible for product formation.     

Investigating the performance characteristics of the barrier discharge ionization detector and comparison to the flame ionization detector for the gas chromatographic analysis of volatile and semivolatile organic compounds

Abstract

The response behavior and performance characteristics of the recently introduced barrier discharge ionization detector (BID) for gas chromatography (GC-BID) were investigated by analyzing different classes of organic compounds such as alcohols, alkanes, cycloaliphatic compounds, polycyclic aromatic hydrocarbons (PAHs), and others. The results obtained by GC-BID were compared with those of gas chromatography with flame ionization detection (GC-FID), aiming to demonstrate the particular merits of the new BID detector over the well-established FID. The response of the BID not only was found to be strongly dependent on the detector settings, but also shows a high dependence on the analyte class and the individual analyte. The sensitivity of the BID detector compared to the FID was higher by a factor of ca. 4 on average when considering all compounds analyzed. The relative standard deviation (RSD) was better than 5% for the majority of the cases. The BID detector showed better precision (lower RSD) in comparison with the FID for the investigated compounds. Linear calibrations were obtained for the analytes over more than four orders of magnitude with coefficients of determination typically higher than 0.999 and the limits of detection varied from 0.04 to 1.48?ng/s for the GC-BID.     

Reversed phase HPLC coupled on-line to GC by the vaporizer/precolumn solvent split/gas discharge interface; analysis of phthalates in water

Reversed phase liquid chromatography (RPLC) was coupled on-line to gas chromatography (GC) via the vaporizer chamber/preco-lumn solvent split/gas discharge interface outlined recently. Water-containing eluents were driven into a vaporizer chamber at 300°C by the LC pump. The Vapors were removed through an early vapor exist by the carrier gas. Solvent/solute separation occurred in hte retaining precolumn. Special attention was paid to the parame-ters determining the losses of the most volatile compounds. The oven temperature during transfer was lowered close to the dew point of the eluent (the temperature at which recondensation occurs) in order to maximise the retention power of the retaining precolumn. The dew point depends on the transfer rate, the gas flow rate, and the gas inlet pressure. Sometimes even better retention of the vola-tiles was observed at temperatures below the dew point, i.e. despite partial reconsideration. The method was applied to the analysis of phthalates in drinking and surface waters. The detection limits, using MS, were 5–10 ng/l.     

Solid phase extraction with silicon dioxide microspheres for the analysis of polychlorinated biphenyls in environmental water samples prior to gas chromatography with electron capture detector

This paper describes a simple, rapid and sensitive method for the determination of polychlorinated biphenyls (PCBs) including PCB-28, PCB-52, PCB-101, PCB-138, PCB-153 and PCB-180 using silicon dioxide microspheres solid phase extraction cartridge prior to gas chromatography with electron capture detector. The experimental results indicate that there were excellent linear relationships between the peak areas and the concentrations of polychlorinated biphenyls, and the linear ranges were in the concentration range of 0.1 to 30?µg?L^?1 with the correlation coefficients in the range of 0.9962 to 0.9998. The detection limits were in the range of 0.003 to 0.019?µg?L^?1. The precisions of the proposed method were below 10% (n?=?6). The enrichment factors, described as the ratio of the slope of the calibration curves with and without extraction, were in the range of 605.2 to 1414.6. The proposed method was used to analyse the real water samples, and satisfactory spiked recoveries in the range of 80 to 117% were achieved. These results demonstrated that silicon dioxide microspheres without modification were good adsorbent for the enrichment of polychlorinated biphenyls and the developed method were of great value and would be a good alternative for the routine analysis of polychlorinated biphenyls in the future.     

An advanced gas/vapor permeation system for barrier materials: Design and applications to poly(ethylene terephthalate)

A new gas/vapor mixture permeation system is described to investigate the effect of organic molecules on oxygen (O₂) and carbon dioxide (CO₂) transport in barrier materials. Methanol vapor was considered as a flavor simulant mainly because of its conveniently high diffusion coefficient, which makes the experimental time accessible. A highly accurate syringe pump was used to introduce a desired activity level of vapor into gas feed stream. Adsorption of methanol on high energy surfaces is carefully characterized to prevent underestimation of methanol permeability. A special permeation cell was also developed to study the effect of interacting vapors on O₂ and CO₂ transport in barrier materials. Systematic permeation measurements were conducted for binary and ternary gas/vapor permeation measurements (e.g., MeOH/O₂ and O₂/CO₂/MeOH) to verify the feasibility of our new vapor/gas permeation system. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Convex hull: A new method to determine the separation space used and to optimize operating conditions for comprehensive two-dimensional gas chromatography

It is important to develop methods of optimizing the selection of column sets and operating conditions for comprehensive two-dimensional gas chromatography. A new method for the calculation of the percentage of separation space used was developed using Delaunay's triangulation algorithms (convex hull). This approach was compared with an existing method and showed better precision and accuracy. It was successfully applied to the selection of the most convenient column set and the geometrical parameters of second column for the analysis of 49 target compounds in wastewater.     

A three‐phase solvent extraction system combined with deep eutectic solvent‐based dispersive liquid–liquid microextraction for extraction of some organochlorine pesticides in cocoa samples prior to gas chromatography with electron capture detection

A sample pretreatment method based on the combination of a three‐phase solvent extraction system and deep eutectic solvent‐based dispersive liquid–liquid microextraction has been introduced for the extraction of four organochlorine pesticides in cocoa samples before their determination by gas chromatography‐electron capture detection. A mixture of sodium chloride, acetonitrile, and potassium hydroxide solution is added to cocoa bean or powder. After vortexing and centrifugation of the mixture, the collected upper phase (acetonitrile) is removed and mixed with a few microliters of N,N‐diethanol ammonium chloride: pivalic acid deep eutectic solvent. Then it is rapidly injected into deionized water and a cloudy solution is obtained. Under optimum conditions, the limits of detection and quantification were found to be 0.011‐0.031 and 0.036‐0.104 ng/g, respectively. The obtained extraction recoveries varied between 74 and 92%. Also, intra‐ (n = 6) and interday (n = 4) precisions were less than or equal to 7.1% for the studied pesticides at a concentration of 0.3 ng/g of each analyte. The suggested method was applied to determine the studied organochlorine pesticide residues in various cocoa powders and beans gathered from groceries in Tabriz city (Iran) and aldrin and dichlobenil were found in some of them.     

Multiresidue method for the analysis of more than 140 pesticide residues in fruits and vegetables by gas chromatography coupled to triple quadrupole mass spectrometry

A new multiresidue method has been developed and validated for the determination of more than 140 pesticide residues in cucumber and orange by gas chromatography coupled to triple quadrupole mass spectrometry (GC-QqQ-MS/MS) in a single run of 25.50 min. The triple quadrupole (QqQ) analyzer simultaneously operated in the selected reaction monitoring (SRM) and selected ion monitoring (SIM) modes, acquiring two or three transitions per compound. Samples were extracted by the application of a single-phase extraction of 10 g of sample with acetonitrile containing 1% of acetic acid, followed by a liquid-liquid partition formed by the addition of 4 g of MgSO(4) and 1 g of NaOAc. A dispersive solid-phase extraction (D-SPE) with primary secondary amine (PSA) was applied to clean up the extracts. A final concentration step was included in order to increase sensitivity in the instrumental analysis. The method was properly validated in each matrix in a wide dynamic range (10-400 microg kg(-1)): this work relies on a new quantification strategy by the use of two calibration curves to increase the dynamic range, which permitted reduction of sample dilutions and increase in sample throughput. Recovery was studied at three concentration levels (11.5, 50.0, and 150.0 microg kg(-1)), yielding values in the range 70-110% with precision values, expressed as relative standard deviation (RSD), lower than 20 and 25% for the intraday and interday precision, respectively. Limits of quantification (LOQs) were established at 10 microg kg(-1), the lowest maximum residue level (MRL) value set by the European Union in vegetables. The method was successfully applied to the analysis of pesticide residues in real samples from the southeastern Spain. Copyright (c) 2008 John Wiley & Sons, Ltd.     

Optimized cleanup method for the determination of short chain polychlorinated n-alkanes in sediments by high resolution gas chromatography/electron capture negative ion-low resolution mass spectrometry

The performances of three adsorbents, i.e. silica gel, neutral and basic alumina, in the separation of short chain polychlorinated n-alkanes (sPCAs) from potential interfering substances such as polychlorinated biphenyls (PCBs) and organochlorine pesticides were evaluated. To increase the cleanup efficiency, a two-step cleanup method using silica gel column and subsequent basic alumina column was developed. All the PCB and organochlorine pesticides could be removed by this cleanup method. The very satisfying cleanup efficiency of sPCAs has been achieved and the recovery in the cleanup method reached 92.7%. The method detection limit (MDL) for sPCAs in sediments was determined to be 14 ng g⁻¹. Relative standard deviation (R.S.D.) of 5.3% was obtained for the mass fraction of sPCAs by analyzing four replicates of a spiked sediment sample. High resolution gas chromatography/electron capture negative ion–low resolution mass spectrometry (HRGC/ECNI–LRMS) was used for sPCAs quantification by monitoring [M−HCl]⁻ ions. When applied to the sediment samples from the mouth of the Daliao River, the optimized cleanup method in conjunction with HRGC/ECNI–LRMS allowed for highly selective identifications for sPCAs. The sPCAs levels in sediment samples are reported to range from 53.6 ng g⁻¹ to 289.3 ng g⁻¹. C₁₀- and C₁₁-PCAs are the dominant residue in most of investigated sediment samples.     

A QuEChERS‐based extraction method for the residual analysis of pyraclofos and tebufenpyrad in perilla leaves using gas chromatography: application to dissipation pattern

The objective of this work was to establish a simple extraction method for the residual analysis of pyraclofos and tebufenpyrad in Perilla leaves. A QuEChERS (quick, easy, cheap, effective, rugged and safe) method was used for extraction using ethyl acetate as an extraction solvent, and cleanup was carried out using dispersive solid‐phase extraction technique. The samples were analyzed using gas chromatography with nitrogen phosphorous detector and confirmed by gas chromatography–mass spectrometry. The linearity was excellent (r² = 1.0) in matrix‐matched calibration for both pesticides. The recoveries at two fortification levels were 80.76–95.38% with relative standard deviation lower than 5%. The limits of detection and limits of quantification were 0.01 and 0.033 mg/kg for both pesticides, respectively. The results revealed that the dissipation pattern of pyraclofos and tebufenpyrad followed first‐order kinetics. The pyraclofos and tebufenpyrad residues declined to a level below the maximum residue limits within 14 day between the last application and harvesting. We suggest that pyraclofos and tebufenpyrad could be used efficiently on perilla leaves under the recommended dosage conditions. Copyright © 2012 John Wiley & Sons, Ltd.     

A rapid method for the quantification of urinary phthalate monoesters: A new strategy for the assessment of the exposure to phthalate ester by solid‐phase microextraction with gas chromatography and tandem mass spectrometry

In the following work, a new method for the analysis of the phthalate monoesters in human urine was reported. Phthalate monoesters are metabolites generated as a result of phthalate exposure. In compliance with the dictates of Green Analytical Chemistry, a rapid and simple protocol was developed and optimized for the quantification of phthalate monoesters (i.e., monoethyl phthalate, monoisobutyl phthalate, mono‐n‐butyl phthalate, mono‐(2‐ethylhexyl) phthalate, mono‐n‐octyl phthalate, monocyclohexyl phthalate, mono‐isononyl phthalate) in human urine, which entails preceding derivatization with methyl chloroformate combined with the use of commercial solid phase microextraction and the analysis by gas chromatography‐triple quadrupole mass spectrometry. The affinity of the derivatized analytes toward five commercial coatings was evaluated, and in terms of analyte extraction, the best results were reached with the use of the divinylbenzene/carboxen/polydimethylsiloxane fiber. The multivariate approach of experimental design was used to seek for the best working conditions of the derivatization reaction and the solid phase microextraction, thus obtaining the optimum response values. The proposed method was validated according to the guidelines issued by the Food and Drug Administration achieving satisfactory values in terms of linearity, sensitivity, matrix effect, intra‐ and inter‐day accuracy, and precision.