城市生活垃圾焚烧体系化学热力学平衡分析

采用化学热力学平衡分析方法，分析城市生活垃圾焚烧体系污染物的排放特性。主要计算了聚氯乙烯（PVC）及典型城市垃圾焚烧过程氯元素的化学平衡组成及其浓度，同时研究了脱氯剂对PVC及垃圾中氯转化的影响。计算结果表明，PVC热态反应的主要产物是HCl气体，在加入脱氯剂后温度低于600℃时，脱氯剂对HCl的脱除作用很明显；城市生活垃圾热解和燃烧过程中在温度超过600 ℃，垃圾中的有机氯和无机氯都将转化为HCl气体，而此时脱氯剂失去效果。由计算结果得到控制HCl生成，消除二口恶英污染物的生成反应工艺条件。     

Surface Prechlorination of Anatase TiO2 for Enhanced Photocatalytic Oxidation of Toluene and Hexane

We report the influence of prechlorination of TiO₂ powder on the activity for the photocatalyzed oxidation of hydrocarbons (toluene, hexane) and oxygenates (acetone, butan‐1‐ol). Water‐ and HCl‐pretreated catalyst are prepared by impregnation of TiO₂ powder in H₂O and in HCl solutions, respectively, followed by drying at room temperature. X‐Ray photoelectron spectroscopy (XPS) analysis demonstrates the surface prechlorination efficiency: 1 g of TiO₂ impregnated with 3 ml of 3n HCl solution results in a chlorine surface concentration of 1.6%. Prechlorination results in a photo‐oxidation‐rate enhancement for toluene and hexane, no change for butan‐1‐ol, and inhibition for acetone. This pattern is the same as that demonstrated earlier by us when these reactants are co‐fed with the chlorine source trichloroethylene (TCE).     

Electron beam treatment of chloroethylenes/air mixture in a flow reactor

Decomposition of chloroethylenes under electron beam irradiation in a flow reactor has been studied with different reaction environments, various initial concentrations and in the presence and absence of vaporized water. Three chlorinated ethylenes—dichloroethylene (DCE), trichloroethylene (TCE), perchloroethylene (PCE)—were used as model chlorocarbons. The degree of decomposition was 48% for DCE, 98% for TCE and 90% for PCE in air reaction environment at an initial concentration of 2000 ppm and a dose of 18–20 kGy irradiation. In the presence of water vapor (5600 ppm) decomposition of TCE was about 10% higher than in dry air. The main products were found to be CO, CO₂, HCl, dichloroacetic acid (DCAA), dichloroacetyl chloride (DCAC) and dichloroethyl ester acetic acid (DEAA). DCAA, DCAC and DEAA were identified as chloro-oxygenated hydrocarbons, which could be decomposed with CO and CO₂ production. Concentration profiles show that intermediate products and yields of CO and CO₂ decrease with decreasing number of chlorine substitutions in the initial hydrocarbons.     

Study on the Relationship between the Emission of Chlorine and UV/VIS Sensitive Organic Matter from Heating MSWI Baghouse Ash: Using an Optical UV/VIS Spectrometer as the On‐Line Monitoring Sensor

In this study the baghouse ash (fly ash) from municipal solid waste incineration (MSWI) plants was heated in a fixed bed reactor, from 25 °C to 800 °C. An optical fiber UV/VIS spectrometer was employed as the real‐time monitor to probe the emission behaviors of organic compounds. A two‐dimensional (2D) correlation technique was used to specify organic matter existing in exhausted gas. Three adsorbents, including water, acetone and cyclohexane, were used to adsorb the organic and molecular chlorine in the gas emitted from the reactor. Concentrations of molecular chlorine (Cl₂), total organic carbon (TOC), and total inorganic carbon (TIC) in these adsorbents were analyzed to evaluate the reactions occurring in fly ash. We have found that generation temperatures of molecular chlorine were found mainly at 200 °C and 750 °C, which are attributed to the dechlorination of chlorinated‐organic compounds and vaporization of heavy metal chlorides, respectively. 2D correlation UV/VIS spectra are useful to extract valuable information from the one‐dimensional UV/VIS of emitted gas. The identified organic species would be diethyl‐amine, dibenzo‐p‐dioxin, thioxanthone, 1,4‐dichloro‐anthraquinone, benzene, 1‐naphthalene azo, azulene, dibenzanthrone, 1‐chloro‐4‐notroso‐benzene and 4‐nitro‐toluene. The emission behaviors of dibenzo‐p‐dioxin, thioxanthone, azulene and dibenzanthrone were reported, and we concluded that the chlorine emission is almost always earlier than the release of these UV/VIS‐sensitive organic compounds.     

Reduction of NO2 in Flue Gas by CO and Propylene over CuO‐CeO2/SiO2 in the Presence of O2

Catalytic reduction of NO₂ with CO and/or propylene in the presence of NO and excess oxygen, a model mixture for flue gas, was studied over a series of CuO‐CeO₂/SiO₂ catalysts between 120–260 °C. The effect of HCl, an impurity in flue gas, on the activity of the catalysts was evaluated. It was found that a binary oxide catalyst, 2% CuO‐8% CeO₂/SiO₂, was active for the reduction of NO₂ by CO and/or propylene. CO was effective for selective reduction of NO₂ in the presence of NO and O₂ in a temperature window between 160–200 °C while propylene was effective at temperature higher than 200 °C. In the presence of HCl, the activity of the catalyst for reduction of NO₂ with CO was irreversibly deactivated. However, the activity for reduction of NO₂ with propylene was not influenced by HCl.     

The infrared chemiluminescent reaction of Cl atoms with H2CO

The reaction Cl + H₂CO → HCl + HCO has been studied at 295 K. Chlorine atoms were produced via the infrared laser induced dissociation of CCl₃F, using a pulsed CO₂ TEA laser. Using HCl infrared chemiluminescence as the diagnostic, we find the rate constant to be 7.4 ± 0.7 × 10^?11 cm³/molecule sec, in good agreement with several recent studies. An evaluation of TEA laser photolysis as a technique for the generation of chlorine atoms is made, and the relationship of this experiment to recent theories of infrared laser induced chemistry is discussed.     

Abatement of Gaseous Xylene Using Double Dielectric Barrier Discharge Plasma with In Situ UV Light: Operating Parameters and Byproduct Analysis

Ultraviolet (UV) light with a wavelength of 254 nm was applied to a double dielectric barrier discharge (DDBD) system to decompose of gaseous xylene. The results show that a significantly synergistic effect can be achieved with the introduction of UV light into the DDBD system. When UV light is applied, the system show a 21.8 % increase in its removal efficiency for xylene at 35 kV with an ozone concentration close to 971 ppmv. The CO _x (x = CO₂ and CO) selectivity of outlet gas rises from 6.54 to 76.2 %. The optimal synergetic effect between UV light and DDBD can be obtained at a peak voltage of 30 kV. The system is robust for humidity, which only slightly reduces the xylene removal efficiency at a high peak voltage (30–35 kV). With the increase of gas flow rate, the removal efficiency for xylene decreases due to a reduced residence time. In addition, the products of xylene degradation were also analyzed. The major products of the degradation were found to be CO₂ and H₂O while byproducts such as O₃ and HCOOH were observed as well.     

Non-Thermal Plasma Assisted Regeneration of Acetone Adsorbed TiO2 Surface

Improvement of indoor air quality regarding volatile organic compounds (VOCs) requires the development of innovative oxidation processes. This paper investigates the coupling of a metal oxide sorbent with non-thermal plasma (NTP) in an especially designed reactor. TiO₂ was selected as model sorbent and acetone was used as model VOC. The analyses of gas phase species at the reactor downstream have been performed using FTIR spectroscopy. In a first step, acetone adsorption on TiO₂ surface under dry air was characterized in terms of total amount adsorbed, as well as reversibly and irreversibly adsorbed fractions. Obtained results were compared and discussed with literature in terms of acetone reactive adsorption on TiO₂ surface. Mesityloxide was proposed as the major compound in the irreversibly adsorbed fraction. In a second time, acetone saturated TiO₂ surface was exposed to NTP surface discharge. Irrespectively of the injected power, <30 % of the initially adsorbed acetone has been recovered as CO, CO₂ and desorbed acetone. Finally, thermal desorptions have been performed. They evidenced that (1) NTP treatment modifies the nature of the adsorbed organic species, (2) mineralization rate is considerably improved. Based on desorbed species temporal profile analysis, carboxylates and more especially formates are suggested as major adsorbed species after NTP treatment (P_inj > 0.2 W). This hypothesis has been evaluated and confirmed. This paper finally evidenced that NTP can be used as an efficient pretreatment technique to promote the mineralization of adsorbed acetone for further thermal treatment.     

Plasma Chemical and Electrical Modeling of a Dielectric Barrier Discharge in Kr–Cl2 Gas Mixtures

This paper reports the study of the Kr–Cl₂ plasma chemistry in terms of the homogenous model of a dielectric barrier discharge and for two kinds of the applied voltage excitation shape. The effect of Cl₂ concentration in the gas mixture, as well as gas pressure and power frequency on the discharge efficiency and the 222 nm photon generation, under typical experimental operating conditions, have been investigated and discussed. Calculations suggest that the overall conversion efficiency from electrical energy to ultraviolet emission in the lamp is in the range of 4.4–12 %, and it will be very affected at high chlorine percentage (>1 %) and high gas pressure (>200 Torr). A comparison between the sinusoidal and the burst excitation waveforms reveals that the burst excitation method provides an enhanced light source performance compared to the sinusoidal wave.     

Degradation of PCDD/Fs in Fly Ash by Vortex-shaped Gliding Arc Plasma

PCDD/Fs in fly ash from municipal solid waste incinerators (MSWIs) can be decomposed in non-thermal plasma, more in particular in a vortex-shaped gliding arc. Typical operating conditions are 10 kV voltage, 40 kΩB external current-limited resistor, 11 L/min tangential gas and 2 L/min axial carrier gas flow rates. Degradation efficiencies of PCDD/Fs are respectively 54.9, 61.7 and 66.8 % on mass basis and 60.7, 73.3 and 70.1 % on toxicity basis under N₂, air and O₂ condition. After treatment the morphology of fly ash has changed: needle-shaped crystals increasing, pores and fragments appearing and high-temperature melting showing which is leaded by direct contact with high-temperature core of arc. The results are explained tentatively by the creation of reactive intermediates leading to dechlorination and oxidation of PCDD/Fs and finally producing end-products such as CO₂, CO, HCl and CH₄.     

Destruction of 2,4 Dichlorophenol in an Atmospheric Pressure Dielectric Barrier Discharge in Oxygen

The processes of degradation of 2,4-dichlorophenol (2,4-DCP) under the action of atmospheric pressure of dielectric barrier discharge (DBD) in oxygen were studied. It was shown that the degradation of 2,4-DCP proceeds efficiently. Degree of decomposition reaches 90%. The degradation kinetics of 2,4-DCP obeys the formal first-order kinetic law on concentration of 2,4-DCP. The effective rate constants depend weakly on the experimental conditions and are equal to ~0.2 s^?1. Based on experimental data, the energy efficiency of decomposition of 2,4-DCP was determined. Depending on the conditions, the energy efficiency was in the range of (8–90) × 10^?3 molecules per 100 eV. The composition of the products was studied by gas chromatography (GC), gas chromatography–mass spectrometry (GC–MS), energy-dispersive X-ray spectroscopy (EDX), attenuated total reflection-fourier transform infrared (ATR-FTIR) spectroscopy, electron spin resonance (ESR) spectroscopy and UV/Visible spectroscopy. It was shown that about ~20% of 2,4-DCP is converted to CO₂, while the other part forms an organic film on the reactor wall. The substance formed is close to the carboxylic acids in chemical composition and exhibits electrical conductivity and paramagnetic properties. Almost all of the chlorine contained in the 2,4-DCP is released into the gas phase. The active species of the afterglow react with liquid hexane, forming the products of its oxidation. Some assumptions regarding the pathway of the process are discussed.     

垃圾焚烧氯对重金属迁移特性的影响

在管式反应炉上，通过加入有机氯（PVC）和无机氯（NaCl）研究了垃圾焚烧时氯对重金属迁移特性的影响。结果表明，在低温下，氯对重金属的挥发几乎没有影响，只有在较高的反应温度下氯才会对重金属的挥发特性产生影响，且垃圾焚烧过程中氯的存在使重金属更易向飞灰或烟气中迁移，垃圾中有机氯对重金属迁移特性的影响要大于无机氯。氯的存在会显著改变分布在飞灰和烟气或底渣和飞灰之间的重金属的分布特性。     

Selective Production of Carbon Monoxide via Methane Oxychlorination over Vanadyl Pyrophosphate

A catalytic process is demonstrated for the selective conversion of methane into carbon monoxide via oxychlorination chemistry. The process involves addition of HCl to a CH₄–O₂ feed to facilitate C?H bond activation under mild conditions, leading to the formation of chloromethanes, CH₃Cl and CH₂Cl₂. The latter are oxidized in situ over the same catalyst, yielding CO and recycling HCl. A material exhibiting chlorine evolution by HCl oxidation, high activity to oxidize chloromethanes into CO, and no ability to oxidize CO, is therefore essential to accomplish this target. Following these design criteria, vanadyl pyrophosphate (VPO) was identified as an outstanding catalyst, exhibiting a CO yield up to approximately 35 % at 96 % selectivity and stable behavior. These findings constitute a basis for the development of a process enabling the on‐site valorization of stranded natural‐gas reserves using CO as a highly versatile platform molecule.     

Photocatalytic degradation of trichloroethylene on platinum ion-doped TiO<Subscript>2</Subscript> under visible light irradiation

Porous platinum ion-doped TiO₂ (Pt–TiO₂) was prepared by a sol–gel method and demonstrated to have superior photocatalytic activity for the photodegradation of gaseous trichloroethylene (TCE) under visible light (VL) irradiation from a xenon lamp equipped with 422-nm cut-off filter. Kinetic studies were performed to clarify the effect of the doping amounts, space times, VL intensity, and mole fractions of TCE, O₂, and H₂O on the degradation of TCE. Under ultraviolet (UV) irradiation, the photocatalytic activity of Pt–TiO₂ was the same as that of TiO₂, indicating that the doped Pt ion did not act as a recombination center for the photogenerated holes and electrons. Based on the kinetic data and reaction products, we conclude that the photocatalytic degradation of TCE on Pt–TiO₂ under VL irradiation proceeds similarly to TiO₂ under UV irradiation. We also performed the photocatalytic degradation of TCE at the space time of 7.5 × 10⁷ g s mol^?1 in a tubular reactor packed with the Pt–TiO₂ pellets which are more suitable than the Pt–TiO₂ powder for the practical remediation of the contaminated gas. TCE was completely degraded, i.e. 100% conversion was achieved under VL irradiation but only a small quantity of CO₂ was formed with the stoichiometric ratio of [CO₂]_formed/[TCE]_degraded of ca. 0.33. By switching the gas stream containing TCE to humid air, more CO₂ was formed, indicating that the dichloroacetates accumulated on the Pt–TiO₂ surface are photodegradable to CO₂ under VL irradiation.     

Solid-state thermal degradation behaviour of 1-D coordination polymers of Ni(II) and Cu(II) bridged by conjugated ligand

Monometallic complexes [Cudadb·yH₂O]_n (2) and [Nidadb·yH₂O]_n (3) and heterobimetallic complex [Cu_0.5Ni_0.5dadb·yH₂O]_n (4) {where dadbH₂ = 2,5-Diamino-3,6-dichloro-1,4-benzoquinone (1); y = 2–4; n = degree of polymerization} were characterized by elemental analysis, atomic absorption spectroscopy, infrared spectroscopy (FTIR) and powder X-ray diffraction. The thermal behaviour of the complexes was studied by thermal analysis (TG/DTA) under air as well as under helium atmospheres. The released gaseous products were investigated by evolved gas analysis performed by an online coupled mass spectrometer (TG/DTA-MS). Thermal degradation of 2 under helium atmosphere is distributed over five steps, whereas 3 and 4 exhibited only four degradation steps due to overlap of second and third degradation steps of into one major step. All the complexes exhibit three steps degradation under air. The complex 2 loses NH group in the second and HCl/Cl₂, CO groups simultaneously in third steps of decomposition under helium, whereas it loses NH and CO groups simultaneously in low temperature region of second step of degradation under air atmosphere as the loss of CO group is facilitated by air. EGA-MS under air and helium atmospheres shows that HCl, CO/CO₂ and (CN)₂ fragments are lost simultaneously at multiple steps, and not successively as predicted earlier. Rate of evolution of most evolved gases exhibits several maxima as a consequence of degradation followed by recombination reactions. Final residues under air and helium atmospheres correspond to the metal oxides and metals along with some carbonaceous matter.     

Chlorinated Organic Compounds Decomposition in a Dielectric Barrier Discharge

The decomposition of chlorinated volatile organic compounds by non-thermal plasma generated in a dielectric barrier discharge was investigated. As model compounds trichloroethylene (TCE) and 1,2-dichloroethane (DCE) were chosen. It was found that TCE removal exceeds 95% for input energy densities above 0.2 eV/molecule, regardless of the initial concentration of TCE, in the range 100–750 ppm. On the other hand, DCE was more difficult to decompose, the removal rate reached a maximum of 60% at the highest input energy used. For both investigated compounds the selectivity towards carbon dioxide was significantly influenced by their initial concentration, increasing when low concentrations were used. The gas flow rate had also an effect on CO₂ selectivity, which is higher at low flow rate, due to the higher residence time of the gas in the plasma. The best values obtained in these experiments were around 80%.     

Steam Plasma Methane Reforming for Hydrogen Production

Reactions of methane with water and CO₂ in thermal plasma generated in a special plasma torch with a water-stabilized arc were investigated. Steam plasma with very high enthalpy and low mass flow rate was produced in a dc arc discharge which was in direct contact with water vortex surrounding the arc column. Composition of produced gas, energy balance of the process and its efficiency were determined from measured data. The output H₂/CO ratio could be adjusted by a choice of feed rates of input reactants in the range 1.1–3.4. Depending on experimental conditions the conversion of methane was up to 99.5%, the selectivity of H₂ was up to 99.9%, and minimum energy needed for production of 1 mol of hydrogen was 158 kJ/mol. Effect of conditions on process characteristics was studied. Comparison of measured data with results of theoretical computations confirmed that the reforming process produces gas with composition which is close to the one obtained from the thermodynamic equilibrium calculations. Relations between process enthalpy, composition of produced syngas and process characteristics were determined both theoretically and experimentally.     

Extraction of gadolinium from El-Garra El-Hamra rare-earth cake,South Western Desert,Egypt

The study area of El-Garra El-Hamra is one of the igneous masses located in the southern part of the Western Desert of Egypt. This work has been carried out to investigate the process of gadolinium separation from REEs cake obtained from El-Garra El-Hamra ore concentrate. It is considered as a new approach in the Nuclear Materials Authority of Egypt. Firstly; the optimum leaching conditions achieved are 200 gm/L H₂SO₄, 1/2 solid/liquid ratio, 4 h agitation time,?125 mesh size and at 90 ^°C temperature. Then by solvent extraction method using 1 mol/L D2EHPA middle REEs were extracted. The organic extractant was stripped by using 2 mol/L HCl and Gd pregnant solution was obtained. Then, the relevant optimum factors were 0.3 mol/L D2EHPA diluted by kerosene, 10 min contact time, and 4/1 organic/aqueous ratio giving 87 % Gd extraction. Then, the scrubbing of the loaded extractant was by 1 mol/L HCL followed by Gd stripping using 5 M HCl, contact time of 30 min and 1/3 organic/aqueous ratio. The strip solution was subjected to evaporation and little amount was dried to obtain GdCl₃ powder having a purity of about 81 % associated with YCl₃ 4 %.     

Theoretical Study of the Water-Gas Shift Reaction Catalyzed by Tungsten Carbonyls

A density functional theory calculation has been carried out to investigate the mechanism of W(CO)₆ and W₂(CO)₁₀ catalyzed water-gas-shift reaction (WGSR). The calculations indicate that the bimetallic catalyst (W₂(CO)₁₀) would be likely to be more highly active than the mononuclear metal-based catalyst (W(CO)₆) due to the possibility of metal–metal cooperativity in reducing the barriers for the WGSR. The energetic span model is a tool to compute catalytic turnover frequencies (TOFs) which is the traditional measure of the efficiency of a catalyst. The one with the highest efficiency usually gives the highest TOF. The bimetallic catalyst (W₂(CO)₁₀) exhibits high catalytic activity towards WGSR due to the highest value of the calculated TOF (3.62 × 10^?12 s^?1, gas phase; 8.74 × 10^?15 s^?1, solvent phase⁾, which is higher than the value of TOF (8.96 × 10^?20 s^?1, gas phase; 3.96 × 10^?19 s^?1, solvent phase) proposed by Kuriakose et al. (Inorg Chem 51:377–385, 2012). Our results will be important for designing a better catalyst for the industrially important reaction.     

Reaction and transport effects in the heterogeneous systems for lean gas purification

Sorption of hydrogen chloride gas by active soda and that of hydrogen sulfide gas by calcium oxide are explored by experiment as promising means of removing these detrimental contaminants from fuel gas: active Na₂CO₃ was prepared by the calcination of commercial NaHCO₃ at 200 °C; reactive CaO was formed by decomposing a fine-grained, high-calcium limestone at 830 °C. Techniques with a differential reactor were employed to explore the rate of reaction of HCl with Na₂CO₃ at 500 °C and that of H₂S with CaO at 800 °C. Time-resolved data on the sorbents’ conversion were collected as a function of mean particle size in the range between 0.285 and 1.12 mm. The surface reaction constants, deduced via the tractable model from the initial reaction rates of the two reactions, slightly increase with the increasing particle size. The proposed correlations enable to interpolate or cautiously extrapolate to other isotropic, irregularly shaped solids. The effective diffusivities educed by means of the model from the experimental curves decrease significantly with the increasing conversion and are affected by the particle size in both sorptions. The developed reaction rate equations can conveniently be applied to the design and simulation of the deep dechloridization and the bulk desulfurization of hot producer gas.