Numerical simulation of semi-dry flue gas desulfurization process in the powder-particle spouted bed

Computational fluid dynamics (CFD) combined with the two-fluid model (TFM) was used for simulation of water vaporization and semi-dry flue gas desulfurization process in a two dimensional powder-particle spouted bed (PPSB), on the basis of gas-solid two-phase flow, the mathematical and physical models of water vaporization process and flue gas desulfurization reaction process have been established through reasonable hypothesis and simplification of the system. The numerical method was used to simulate the desulfurization reaction process and the heat and mass transfer in the powder-particle spouted bed. Simulation results indicate that water vaporization rate was high in spout and annular regions. The main area where flue gas desulfurization reaction occurs was annular area, as a result, the maximum value of desulfurization product rate appears in the annulus. Under the same condition, the desulfurization efficiency of simulation value is 75.75% when the value of slurry water content equals 40 kg-H₂O/kg-dry_sorbent, which is close to but greater than the experimental value (75.03%). The desulfurization efficiency of spouted bed increases first and then decreases with the increase of water content of desulfurization slurry, and the optimum slurry water content for desulfurization process in powder-particle spouted bed was obtained by numerical simulation, which was 40 kg-H₂O/kg-dry_sorbent.     

海水烟气脱硫膜吸收单元及工艺研究

以海水作为吸收剂,采用自行研制的中空纤维管式膜接触器作为吸收单元,进行膜吸收法海水烟气脱硫过程模拟试验研究.考察膜接触器结构、膜填充密度、膜吸收单元工艺方式、模拟烟气SO2浓度、温度、气液流量等因素对脱硫效率的影响.结果表明,提高烟气温度、海水流量、膜接触器内气液分布均匀程度、气液相有效接触面积、增加膜吸收级数,均有利于提高脱硫率;烟气流量及SO2浓度的增大不利于SO2的脱除;烟气流经管程的气液流程方式利于提高脱硫率,但是气阻大,进气压力高,工程化应用难以实现.提高膜材料传质特性和优化设计膜接触器结构是提高膜吸收法烟气脱硫效率的根本途径.     

Response kinetics of a fiber-optic gas sensor using Pt/WO3 thin film to hydrogen

Response kinetics of a fiber-optic hydrogen gas sensor in air- and inert-atmosphere were characterized. The sensor is mainly based on the evanescent field interaction in hydrogen sensitive cladding which is used Platinum-supported tungsten trioxide (Pt/WO₃). When the sensor was exposed to 1 vol.% H₂/air and H₂/N₂ gas, the changes in optical power propagating through the fiber were about 30% and 50%, respectively. The detection limit was about 0.1 vol.% in air-atmosphere. The humidity dependence of the response kinetics was also evaluated. While the response speed in N₂-atmosphere was accelerated, the speed in air-atmosphere was suppressed by the humidity.     

Fe-Mn/TiO2低温NH3-SCR脱硝催化剂的SO2中毒机理

Fe-Mn/TiO₂低温脱硝催化剂具有较高的低温活性和热稳定性,但抗SO₂能力差,不能满足工业应用要求。目前对于SO₂中毒位点以及中毒机理仍不明确。通过浸渍法制备了Fe-Mn/Ti、Fe/Ti、Mn/Ti,并在SO₂或NH₃-SCR气氛下对催化剂进行预硫化,通过TPD、H2-TPR、XRD、FTIR、XPS等表征手段对预硫化前后的样品进行表征,发现Ti、Fe/Ti、Mn/Ti和Fe-Mn/Ti催化剂预硫化后,Ti均发生硫酸化。在NH₃-SCR气氛比在SO₂气氛下催化剂中毒更严重,Fe加入后与Mn形成复合氧化物,改变Mn的存在状态,抑制Mn的硫酸化,但并没能阻止Ti的硫酸化。因此催化剂的抗毒性不仅要防止活性组分中毒,也需要防止载体中毒。     

Dissociation process of CH4/H2 gas mixture during EACVD

The dissociation process of CH₄/H₂ gas mixture during EACVD has been investigated using Monte Carlo simulation for the first time. The electron velocity distribution and H₂ dissociation were obtained over a wide range: 100<E/N<2000 Td. The variation of CH₄ dissociation with CH₄ concentration in the filling gas has been simulated. The electron velocity profile is asymmetric for the component parallel to the field. Most electrons possess non-zero velocity parallel to the substrate. The number of atomic H is a function of E/N. There are two peaks at E/N=177 Td and 460 Td. The appropriate E/N is suggested to be 500–800 Td for low temperature deposition. The main diamond growth precursor is proposed to be CH₃ and CH₃⁺.     

Electrical and spectroscopic properties of Ti0.2 Sn0.8O2 solid solution for gas sensing

In this work we report the synthesis, microstructure, electric and spectroscopic properties, and sensing performances of Ti_xSn_1 − xO₂ (x = 0.1, 0.2, 0.3, 0.5, 0.7, 0.9) nano-powders and of SnO₂ and TiO₂ reference samples, prepared via sol-gel route starting from metal-organic precursors working in hydro-alcoholic media. Actually, the attention is particularly focused on properties of the sample with x = 0.2, in comparison with ones of the other solid solutions and of the single oxides. Indeed, this solid solution showed a borderline behaviour between that of the solid solution with x = 0.1 and that of the other solid solutions with x ≥ 0.3. An abrupt change in the structural, electrical and spectroscopic properties has been observed, passing from sample with x = 0.1, showing a behaviour very similar to that of SnO₂, to one x = 0.3 showing a behaviour very similar to that of TiO₂. The borderline properties of the mixed oxide with x = 0.2 represent the expected continuous transition among the two behaviours.     

A scheme for solving strongly coupled chemical reaction equations appearing in the removal of SO2 and NOx from flue gases

The removal of NO_x from mixtures of NO-NO₂-N₂ and NO-NO₂-O₂-H₂O is discussed theoretically in this study, and the removal of ₂SO and xNO is further discussed when a gas system of NO_x-N₂-O₂-H₂O contains CO₂ and SO₂. The involved chemical reaction rate equations in the process of SO₂/NO_x removal are solved numerically using Treanor's method, in which a scheme separating chemical reactions into fast and slow groups has been proposed for improving the numerical stability. Numerical results show that the contribution of ion reactions to xNO removal is negligible, and that high temperature is not beneficial for the NO oxidation. However, high concentration of O₂ is conducive to the NO oxidation. Addition of water facilitates the NO_x removal, and increasing water vapor concentration enhances the NO_x removal efficiency; inclusion of CO₂ and SO₂ into the system favors the NO removal.     

The effect of Au and Pt nanoclusters on the structural and hydrogen sensing properties of SnO2 thin films

Au and Pt nanoparticle modified SnO₂ thin films were prepared by the sol-gel method on glass substrates targeting sensing applications. Structural and morphological properties of these films were studied using X-ray Diffraction and Scanning Electron Microscopy. It was proved that the films crystallized in tetragonal rutile SnO₂ crystalline structure. Scanning Electron Microscopy observations showed that the metallic clusters' dimensions and geometry depend on the kind of the metal (Au or Pt) while SnO₂ films surface remains almost the same: nanostructured granular very smooth. Optical properties of the films were studied using UV-visible spectroscopy. The modified SnO₂ films were tested as hydrogen sensors. The response of SnO₂, SnO₂-Au and SnO₂-Pt thin films against hydrogen was investigated at different operating temperatures and for different gas concentrations. The addition of metal nanoparticles was found to decrease the detection limit and the operating temperature (from 180 °C to 85 °C), while increasing the sensing response signal.     

Effect of density and thickness on H2-gas sensing property of sputtered SnO2 films

Undoped and Pd-doped SnO₂ films were deposited under various conditions for the investigation of the effect of Pd doping, porosity, and thickness on their H₂ gas sensing properties. The temperature of the substrate and the pressure of the discharge gas were varied. All films formed were composed of columns with thicknesses between 20 and 30 nm. The film density decreased as the discharge gas pressure increased and the substrate temperature decreased. It showed values between 4.2×10³ and 7.0×10³ kg/m³ depending on the deposition condition. Low film density and Pd doping resulted in high sensitivity and fast response. The largest sensitivity was observed for a Pd-doped film with a low density of 4.7×10³ kg/m³ and a thickness of 20 nm.     

Effects of N2-annealing conditions on the sensing properties of Pt/HfO2/SiC Schottky-diode hydrogen sensor

Hafnium oxide (HfO₂) used as the gate insulator of metal-insulator-SiC Schottky-diode hydrogen sensors is annealed in nitrogen at different temperatures and durations for achieving a better performance. The hydrogen-sensing properties of these samples are compared with each other by taking measurements under various temperatures and hydrogen concentrations using a computer-controlled measurement system. The sensor response of the device is found to increase with the annealing temperature and time because higher annealing temperature and longer annealing time can enhance the densification of the HfO₂ film; improve the oxide stoichiometry and facilitate the growth of an interfacial layer to give better interface quality, thus causing a significant reduction of the current of the sensor under air ambient. The effects of hydrogen adsorption on the barrier height and conduction mechanism of the devices are also investigated.     

The influence of flue gas recirculation on oxy-oil combustion in an existing furnace

Oxy-fuel combustion has received increasing attention as one of the major solutions for CO₂ capture. This study aimed to obtain a better understanding on the oxy-oil firing process and to gain experience handling flue gas recirculation. A 300 kW_th multi-fuel combustion test furnace at National Cheng-Kung University in Tainan, Taiwan was chosen as the experimental facility. This experimental study had successfully converted a conventional air-fired furnace to operate on oxy-fuel firing with various operating conditions. Oxygen-enriched combustion and oxy-fuel combustion tests were conducted. The effects of oxygen enrichment, flue gas recirculation, fuel type, and thermal loading on the operational characteristics of the furnace such as temperature distribution, pressure variation, and emission characteristics were examined and discussed. Several concerns about a conventional air-fired furnace adapted for oxy-fuel combustion were scrutinized, including optimization of flue gas recirculation for better combustion efficiency, higher SO₂ concentration in the flue gas under oxy-fuel operation, and air leakage coming from negative pressure operation. These findings provided valuable data to improve the performance of oxy-fuel combustion and to allow better conceptual designs in future development.     

离子液体中阴阳离子的特性对其吸收二氧化硫的影响

SO_2是一种无色、有强烈刺激性气味的气体,弥散在空气中的SO_2对人体健康、生态环境有着严重的危害,是导致空气质量不断恶化的主要大气污染物之一。人为造成的SO_2污染物的主要来源有燃料燃烧、工业生产、交通运输等,其中燃料燃烧占70%。因此,削减和控制燃料燃烧所产生的SO_2的排放是我国能源利用和环保领域的重要研究方向,烟气脱硫是应对烟气中SO_2排放的有效途径。湿法烟气脱硫是目前应用最广泛的方法,占世界安装烟气脱硫机组总容量的85%,采用该方法处理的烟气占总处理量的80%。在湿法烟气脱硫技术中比较实用的主要包括钙法脱硫、有机胺脱硫、海水脱硫。其中,钙法脱硫的脱硫效率高,对煤种的适应性较强,但是脱硫会产生CaSO_4沉淀,降低经济效益;有机胺脱硫的系统腐蚀性小,副产品可生产硫酸,但是胺易挥发,造成吸收剂损失和环境污染;海水法脱硫的工艺简单、运行可靠,但其应用受到地域的影响,并且对环境也会产生一定的影响。离子液体是一种新兴的绿色介质,它具有环保、可再生、结构可调控的优点,为解决传统工艺中的污染问题提供了新方案。在离子液体吸收气体的过程中,吸收液不会因其挥发性而蒸发进入气相,并且可以在较低的温度下完成吸收解吸循环。离子液体的这些优良特性使其在SO_2吸收方面有着极广阔的应用前景。目前,研究者们已合成了一系列胍盐类、咪唑类、醇胺类、吡啶类等离子液体,探究其吸收SO_2的性能与机理,并根据其结构可设计的特点,在离子液体中的阴阳离子上引入各类官能团(如氰基、醚基、氨基、卤素),合成满足特定需求的离子液体,使其高效、可逆、低耗地吸收SO_2。本文总结了近年来各类离子液体吸收SO_2的性能和机理,为系统地认识离子液体在SO_2分离领域的应用提供了帮助;重点阐明了离子液体中阴阳离子的种类、官能化,尤其是酸碱性对其吸收SO_2的影响,这为调整离子液体酸碱性、合理设计离子液体的结构,探索离子液体吸收SO_2的机理,改善其对SO_2的吸收性能有着重要的价值。最后指出了目前研究中存在的问题并且对未来新型离子液体的合成进行了展望。     

Synthesis of TiO2 sol in a neutral solution using TiCl4 as a precursor and H2O2 as an oxidizing agent

Nanosize TiO₂ thin film on glass substrate was obtained through dip-coating method using TiO₂ sol. Suspended nanosize TiO₂ sols with anatase structure in aqueous solution were synthesized by sol–gel method using TiCl₄ as a precursor. TiCl₄ was reacted with an aqueous solution of NH₄OH to form Ti(OH)₄, and H₂O₂ was then added to form peroxo titanic acid. It was further heated in water and converted to TiO₂. The effects of the preparation parameters, viz., pH value of the Ti(OH)₄ gel, concentration of H₂O₂, and heating temperature and time, on the properties of the TiO₂ sol were investigated. The materials were characterized by X-ray diffraction, Fourier transform-infrared spectroscopy, and transmission electron microscopy. The results showed that the primary TiO₂ particles were rhombus with the major axis ca. 10 nm and minor axis ca. 4 nm, and were in anatase structure. The sol was excellent in dispersibility and was stable in neutral and even slight basic conditions for at least 2 years without causing agglomeration. The best preparation condition was optimized with the pH value of Ti(OH)₄ gel at 8, H₂O₂/TiO₂ mole ratio of 2, and heating at 97 °C for 8 h. The transparent adherent TiO₂ film on glass substrates exhibits strong hydrophilicity after illuminating with ultraviolet light and it can be used as an efficient photocatalyst.     

Structural analysis of W3O/WO3 and TiO/TiO2 periodic multilayer thin films sputter deposited by the reactive gas pulsing process

DC reactive sputtering was used to deposit titanium and tungsten-based metal/oxide periodic nanometric multilayers using pure metallic targets and Ar + O₂ gas mixture as reactive atmosphere. The innovative technique namely, the reactive gas pulsing process allows switching between the metal and oxide to prepare a periodic multilayered structure with various metalloid concentrations and nanometric dimensions. The same pulsing period was used for each deposition to produce metal-oxide periodic alternations close to 10 nm. Structure, crystallinity and chemical composition of these films were systematically investigated by Raman spectroscopy, X-ray diffraction and Energy-dispersiveX-ray spectroscopy techniques. The high resolution transmission electron microscopy allowed observing the sharpness of the metal/oxide interfaces and measuring the thickness of each kind of layers. Moreover, the crystalline structure of metal and metal oxide layers was also studied. The difference of reactivity between the two systems leads to periodic β-W₃O/a-WO₃ and face-centered-cubic-TiO/a-TiO₂ multilayers.     

The improvement in ferroelectric performance of (Bi3.15Nd0.85)4Ti3O12 films by the addition of hydrogen peroxide in a spin-coating solution

Chemically synthesized (Bi_3.15Nd_0.85)Ti₃O₁₂ (BNT) films annealed at 650 °C for 15 min were prepared by different approaches to improve their fatigue problem. These approaches involved the selection of substrates with different overlayers, the addition of hydrogen peroxide (H₂O₂) to a spin-coating solution, and annealing in different atmospheres. BNT films on Ti-overlayered substrates had performed badly if processed at oxidation environments. BNT films on TiO₂-overlayered substrates displayed stable and unchanged fatigue endurance if the spin-coating solution was modified by drops of the H₂O₂ solution to lesson the formation of oxygen vacancies in crystalline films. They were also fatigue-free in ferroelectricity after 10¹⁰ switching cycles and had remanent polarization of 24 μm/cm², coercive field of 52 kV/cm, nonvolatile charge density of 13 μC/cm² during relaxed fatigue tests, and leakage current of 10^− 6 A at 3 V.     

The effect of chemical surfactants on the absorption performance during NH3/H2O bubble absorption process

The objectives of this paper are to visualize the bubble behavior by shadow graphic method, to examine the effect of surfactants on the bubble type absorption, and to find the optimal conditions to design highly effective compact absorber for NH₃/H₂O absorption system. The initial concentrations of NH₃/H₂O solution and the kinds and the concentrations of surfactants are considered as key parameters. By measuring the absorption rate for each condition, two effects of the addition of surfactants, the Marangoni and the barrier effect, are compared with each other. The results show that the addition of surfactant enhances the absorption performance up to 4.81 times. The experimental correlations of the effective absorption ratio for each surfactant, 2-ethyl-1-hexanol, n-octanol, and 2-octanol, are suggested within ±15, ±10, and ±10%, respectively.     

SnO2纳米颗粒制备及其对溶胶-凝胶Sb:SnO2薄膜性能的影响

以Sn(OEt)2为起始原料,采用水热晶化法合成了分散性良好的金红石结构的SnO2纳米颗粒.采用X射线衍射对其进行了表征,表明SnO2纳米颗粒的结晶性良好,颗粒尺寸小于10nm.将合成的SnO2纳米颗粒均匀分散到SbSnO2镀膜液中,经陈化后制成镀膜溶胶,以溶胶-凝胶浸渍镀膜工艺制备纳米颗粒掺杂SbSnO2薄膜.分别采用范德堡(Van Der Pauw)法、UV/VIS分光光度计和FTIR中红外分析仪测量并分析膜层的导电性能、光学性能及结构特征,研究了导电纳米颗粒添加对SbSnO2薄膜电性能、光学性能和结构的影响.     

The influence of annealing temperatures on the properties of Bi2VO5.5/LaNiO3/Si thin films

Bi₂VO_5.5 ferroelectric thin films were fabricated on LaNiO₃/Si(100) substrate via chemical solution deposition. Ferroelectric and dielectric properties of the thin films annealed at 500-700 °C were studied. The thin film annealed at 700 °C exhibited more favorable ferroelectric and dielectric properties than those annealed at lower temperatures. The values of remnant polarization 2P_r and coercive field E_c for the film annealed at 700 °C are 10.62 µC/cm² and 106.3 kV/cm, respectively. The leakage current of the film is about 1.92 × 10^− 8 A/cm² at 6 V. The possible mechanism of the dependence of electrical properties of the films on the annealing temperature was discussed.     

红壤土浸出液中SO42-对铜包钢耐蚀性能的影响研究

本文采用扫描电镜/能谱分析(SEM-EDS)、动电位极化、电化学阻抗谱技术研究了铜包钢接地材料受SO₄^2-浓度影响的腐蚀行为.研究结果表明在含有不同浓度的SO₄^2-的红壤土浸出液浸泡20 d,铜包钢都已出现点蚀现象.随着SO₄^2-浓度从0.05~0.2 mol/L逐渐增加,铜包钢腐蚀程度呈现先增后减弱的趋势,在0.05 mol/L的SO₄^2-浸出液中浸泡20天腐蚀最为严重,已腐蚀至内层钢.由于0.05 mol/L的SO₄^2-浸出液中腐蚀后的铜包钢表面已被较多的不导电的腐蚀产物覆盖,因此实验结果显示其阻抗值最大和腐蚀速率最慢.